EP0002800B1 - Optically active alpha-phenoxypropionic acid dervatives - Google Patents

Optically active alpha-phenoxypropionic acid dervatives Download PDF

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Publication number
EP0002800B1
EP0002800B1 EP78101792A EP78101792A EP0002800B1 EP 0002800 B1 EP0002800 B1 EP 0002800B1 EP 78101792 A EP78101792 A EP 78101792A EP 78101792 A EP78101792 A EP 78101792A EP 0002800 B1 EP0002800 B1 EP 0002800B1
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EP
European Patent Office
Prior art keywords
phenoxy
formula
ester
alkyl
propionic acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
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EP78101792A
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German (de)
French (fr)
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EP0002800B2 (en
EP0002800A1 (en
Inventor
Hans Jürgen Dr. Nestler
Gerhard Dr. Hörlein
Reinhard Dr. Handte
Hermann Dr. Bieringer
Friedhelm Dr. Schwerdtle
Peter Dr. Langelüddeke
Peter Dr. Frisch
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Hoechst AG
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Hoechst AG
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Priority claimed from DE19772758002 external-priority patent/DE2758002A1/en
Application filed by Hoechst AG filed Critical Hoechst AG
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    • A—HUMAN NECESSITIES
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    • A01N39/00—Biocides, pest repellants or attractants, or plant growth regulators containing aryloxy- or arylthio-aliphatic or cycloaliphatic compounds, containing the group or, e.g. phenoxyethylamine, phenylthio-acetonitrile, phenoxyacetone
    • A01N39/02—Aryloxy-carboxylic acids; Derivatives thereof
    • A—HUMAN NECESSITIES
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/06—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings
    • A01N43/08—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom five-membered rings with oxygen as the ring hetero atom
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
    • A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
    • A01N43/20—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom three- or four-membered rings
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
    • A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
    • A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
    • A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
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    • A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
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    • A01N43/74—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with nitrogen atoms and oxygen or sulfur atoms as ring hetero atoms five-membered rings with one nitrogen atom and either one oxygen atom or one sulfur atom in positions 1,3
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    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/12—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, neither directly attached to a ring nor the nitrogen atom being a member of a heterocyclic ring
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    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
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    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/16—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof the nitrogen atom being part of a heterocyclic ring
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    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
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    • A01N47/10—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof
    • A01N47/18—Carbamic acid derivatives, i.e. containing the group —O—CO—N<; Thio analogues thereof containing a —O—CO—N< group, or a thio analogue thereof, directly attached to a heterocyclic or cycloaliphatic ring
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    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
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    • C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
    • C07C41/01—Preparation of ethers
    • C07C41/18—Preparation of ethers by reactions not forming ether-oxygen bonds
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    • C07C59/40—Unsaturated compounds
    • C07C59/58—Unsaturated compounds containing ether groups, groups, groups, or groups
    • C07C59/64—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings
    • C07C59/66—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings
    • C07C59/68—Unsaturated compounds containing ether groups, groups, groups, or groups containing six-membered aromatic rings the non-carboxylic part of the ether containing six-membered aromatic rings the oxygen atom of the ether group being bound to a non-condensed six-membered aromatic ring
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    • C07C67/00—Preparation of carboxylic acid esters
    • C07C67/30—Preparation of carboxylic acid esters by modifying the acid moiety of the ester, such modification not being an introduction of an ester group
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    • C07C69/73—Esters of carboxylic acids having esterified carboxylic groups bound to acyclic carbon atoms and having any of the groups OH, O—metal, —CHO, keto, ether, acyloxy, groups, groups, or in the acid moiety of unsaturated acids
    • C07C69/734—Ethers
    • C07C69/736—Ethers the hydroxy group of the ester being etherified with a hydroxy compound having the hydroxy group bound to a carbon atom of a six-membered aromatic ring
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D213/62—Oxygen or sulfur atoms
    • C07D213/63—One oxygen atom
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    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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    • C07D213/64—One oxygen atom attached in position 2 or 6
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    • C07D263/54—Benzoxazoles; Hydrogenated benzoxazoles
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    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • halogen always means chlorine or bromine.
  • the compounds of formula 1 obtained according to a) or b) can be converted into other compounds of formula I by generally known operations.
  • the latter supply the corresponding amides, hydrazides or thioesters via the acid halides.
  • esterifying the free acids or acid chlorides or by direct transesterification other esters of the formula I are formed.
  • the processes according to the invention deliver end products with an optical purity of at least 60%, corresponding to a proportion of 80% of the D-form.
  • the optical purity of the compounds can be determined by conventional methods, e.g. Recrystallization can be further increased. If these compounds, in particular the esters, are liquid, it is a preferred cleaning process to saponify the esters initially obtained to the corresponding phenoxypropionic acid, to purify them in a manner known per se by recrystallization of any small amounts of the L-form present and then from the largely pure acid to produce the desired compounds of formula I by one of the methods given above.
  • the D-enantiomers according to the invention are distinguished from the racemates described above by a considerably increased herbicidal action. Surprisingly, it was found that the L-enantiomers are practically ineffective after emergence. The effectiveness of the racemates is based practically solely on their content of D-enantiomers.
  • the invention thus also relates to herbicidal compositions which are characterized by a content of an active compound of the formula I which contains less than 20% by weight, preferably less than 10% by weight, in particular less than 5% by weight, of the L-enantiomer in combination with customary auxiliaries - and carriers.
  • the formulation for practical use follows the same methods and with the same additives as are already known for the racemates.
  • Preferred formulations are liquid formulations or ULV formulations.
  • the formulations preferably contain 2-95% of the active ingredients, depending on the type of preparation. Because of their better effectiveness, the required application rate per unit area compared to the racemates can be reduced by up to 60% with the optically active active substances according to the invention; it is generally between 0.01-5 kg / ha, preferably 0.05 to 3 kg / ha.
  • the solvent is then largely distilled off in a water jet vacuum, the residue is taken up in methylene chloride and washed with water. After evaporation of the methylene chloride, the product is distilled in a high vacuum.
  • the remaining residue is fractionated in a high vacuum.
  • the optically active D - (+) compounds (in detail see tables) were tested in field tests in comparison to the corresponding racemates in a post-emergence method against various harmful grasses.
  • the plot sizes were 5 or 10 m 2 ; it was worked with 3 to 4 times repetition.
  • the compounds were formulated as emulsion concentrates and applied in various application rates per hectare at a water rate of 500 l / ha, the amount of liquid, based on 1 ha, being 500 l each.
  • the ED 95 or ED 98 values indicate the active substance dose / ha at which 95% or 98% of the harmful plants are killed (ED “effective dose”).
  • the active ingredient saving is therefore 40 or 43% compared to the racemate. No phytotoxis occurred on the treated sugar beets at any time.
  • the active ingredient savings in the field foxtail control is therefore 41 or 53% in relation to the Racemat.
  • the savings for airport oats are 62%.
  • the active ingredient saving is approximately 42%.
  • the active ingredient saving is therefore 41% compared to the Racemate with the same high level of control success. There was no cultural damage to summer wheat.

Description

Es ist bekannt, daß viele Naturstoffe mit biologischer Wirksamkeit infolge des Vorhandenseins eines oder mehrerer asymmetrischer Kohlenstoffatome optisch aktiv sind, d.h. die Ebene des polarisierten Lichtes nach rechts (+) oder links (-) drehen. Sehr oft weisen diese Verbindungen eine höhere biologische Wirksamkeit auf als entsprechende synthetisch gewonnene, optisch inaktive Verbindungen. Ähnliches gilt für manche synthetisch hergestellte Wirkstoffe wie Pharmazeutika oder Pflanzenschutzmittel mit asymmetrischen C-Atomen, die gewöhnlich bei der Synthese als optisch inaktive Racemate, d.h. Gemische aus gleichen Anteilen der rechts- und links-drehenden Enantiomeren, anfallen. Auch hier wird bei der Isomerentrennung nicht selten gefunden, daß die Wirksamkeit eines der beiden Enantiomeren höher ist als die des Racemats. Ob die links (-)- oder die rechts (+)-drehende Form die jeweils aktive ist und ob überhaupt ein Zusammenhang zwischen Wirkung und optischer Aktivität besteht, läßt sich jedoch nicht vorhersagen.It is known that many natural products with biological activity are optically active due to the presence of one or more asymmetric carbon atoms, i.e. turn the plane of the polarized light to the right (+) or left (-). These compounds very often have a higher biological activity than corresponding synthetically obtained, optically inactive compounds. The same applies to some synthetically produced active substances, such as pharmaceuticals or plant protection products with asymmetric carbon atoms, which are usually synthesized as optically inactive racemates, i.e. Mixtures of equal proportions of the right and left rotating enantiomers are obtained. Here, too, it is not infrequently found in the separation of isomers that the activity of one of the two enantiomers is higher than that of the racemate. However, it cannot be predicted whether the left (-) - or the right (+) - rotating form is the active one and whether there is any connection between effect and optical activity.

Aus der Klasse der p-substituierten a-Phenoxy-propionsäure-Derivate wurden in letzter Zeit Verbindungen bekannt, die wegen ihrer spezifisch grasherbiziden Wirkung von Interesse sind [z.B. DE-OS 22 23 894, DE-OS 24 33 067, DE-OS 25 31 643, DE-OS 26 17 804, DE-OS 26 23 558, DE-OS 25 46 251, DE-OS 24 17487 und DE-OS 26 01 548]. Diese besitzen in Nachbarstellung zur Carbonylfunktion ein asymmetrisches C-Atom, sodaß 2 enantiomere, optisch aktive Formen existieren, die gewöhnlich als D-und L-Form bezeichnet werden.From the class of p-substituted a-phenoxy-propionic acid derivatives, compounds have recently been known which are of interest because of their specific grass herbicidal activity [e.g. DE-OS 22 23 894, DE-OS 24 33 067, DE-OS 25 31 643, DE-OS 26 17 804, DE-OS 26 23 558, DE-OS 25 46 251, DE-OS 24 17487 and DE- OS 26 01 548]. In the position adjacent to the carbonyl function, these have an asymmetric C atom, so that there are 2 enantiomeric, optically active forms which are usually referred to as the D and L forms.

Es wurde nun gefunden, daß die D-Enantiomeren dieser Verbindungen sich durch eine erheblich höhere herbizide Wirksamkeit im Vergleich zu den Racematen auszeichnen.It has now been found that the D-enantiomers of these compounds are distinguished by a considerably higher herbicidal activity compared to the racemates.

Gegenstand der Erfindung sind somit D-(a-Phenoxy-propionsäurederivate der Formel I

Figure imgb0001
in der

  • R eine Gruppe der Formel
    Figure imgb0002
    oder
    Figure imgb0003
  • R1 Wasserstoff, Halogen oder CF3
  • R2 Wasserstoff, (C1-C4)-Alkyl, Halogen oder NO2, mit der Maßgrabe, daß, falls R einen Rest der Formel 11, III oder VI bedeutet, R1 nicht Wasserstoff ist,
  • Z eine Gruppe der Formel
    Figure imgb0004
  • R3H, (C1-C12)-Alkyl, das gegebenenfalls durch 1-6 Halogenatome und/oder durch OH, (C1-C6)-Alkoxy, (C1-C4)-Alkylthio, (C1-C6)-Alkoxy-(C2-C6)-alkoxy, Halogen-(C1-C2)-alkoxy, Methoxy-äthoxy-äthoxy, (C1-C4)-Alkylamino, D-(C1-C4)-alkylamino, Phenyl, Oxiranyl und Phenoxy substituiert ist, wobei letzteres ebenfalls ein- bis zweifach durch Halogen und/oder (C1-C4)-Alkyl substituiert sein kann ; (Cs-C6)-Cycloalkyl oder Halogen-(C5-C6)-cycloalkyl, (C3-C6)-Alkenyl, Halogen-(C3-C6)-alkenyl oder (C5-C6)-Cycloalkenyl, (C3-C4)-Alkinyl, das gegebenenfalls ein oder zweifach durch (C1-C6)-Alkyl, Phenyl, Halogen bzw. (C1-C2-Alkoxy substituiert ist, Phenyl, das gegebenenfalls ein- bis dreifach durch (C1-C4)-Alkyl, (C1-C4)-Alkoxy, Halogen, N02 oder CF3 substituiert ist, Furfuryl, Tetrahydrofurfuryl oder ein Kationäquivalent einer organischen oder anorganischen Base,
  • R4(C1-C6)-Alkyl, das gegebenenfalls durch (C1-C4)-Alkoxy, Halogen oder Phenyl substituiert ist, wobei letzteres ebenfalls ein- bis dreifach durch (C1-C4)-Alkyl und Halogen substituiert sein kann ; (C3-C6)-Alkenyl oder Phenyl, das gegebenenfalls ein- bis dreifach durch (C1-C4)-Alkyl und/oder Halogen substituiert ist,
  • R5 und R6 gleich oder verschieden sind und H, (C1-C6)-Alkyl, Hydroxy-(C1-C6)-alkyl, (C5-C6)-Cycloalkyl oder Phenyl, das gegebenenfalls ein- bis dreifach durch (C1-C4)-Alkyl, (C1-C4)-Alkoxy, Halogen oder CF3 substituiert ist (mit der Maßgabe, daß R5 und R6 nicht gemeinsam Phenyl sind), bedeuten oder gemeinsam eine Methylenkette mit 2, 4 oder 5 Gliedern bilden, in der eine CH2-Gruppe gegebenenfalls durch O, NH oder N(CH3) ersetzt sein kann,
  • R7H oder CH3,
  • RgH, CH3 oder C2H5,
  • R9H, CH3, C2H5 oder Phenyl bedeuten mit der Einschränkung, daß wenn R1 Trifluormethyl, R2 Wasserstoff und R eine Gruppe der Formel II sind, R3 nicht Wasserstoff ist (IT) bzw. mit der Einschränkung, daß in Verbindungen, in denen R die Gruppe der Formel II ist, R3 nur dann H oder unsubstituiertes Alkyl sein kann, wenn R1 oder R2CI in para-Stellung bedeutet (BE, DE, FR, GB, NL, SE).
The invention thus D- (a-phenoxy-i propionsäureder derivatives of the formula I
Figure imgb0001
 in the
  • R is a group of the formula
    Figure imgb0002
     or
    Figure imgb0003
  • R 1 is hydrogen, halogen or CF 3
  • R 2 is hydrogen, (C 1 -C 4 ) -alkyl, halogen or NO 2 , with the proviso that if R is a radical of the formula 11, III or VI, R 1 is not hydrogen,
  • Z is a group of the formula
    Figure imgb0004
  • R 3 is H, (C 1 -C 12 ) -alkyl, which is optionally substituted by 1-6 halogen atoms and / or by OH, (C 1 -C 6 ) -alkoxy, (C 1 -C 4 ) -alkylthio, (C 1 -C 6 ) -alkoxy- (C 2 -C 6 ) -alkoxy, halogen- (C 1 -C 2 ) -alkoxy, methoxy-ethoxy-ethoxy, (C 1 -C 4 ) -alkylamino, D- (C 1 -C 4 ) alkylamino, phenyl, oxiranyl and phenoxy is substituted, the latter also being able to be substituted once or twice by halogen and / or (C 1 -C 4 ) alkyl; (C s -C 6 ) cycloalkyl or halogen (C 5 -C 6 ) cycloalkyl, (C 3 -C 6 ) alkenyl, halogen (C 3 -C 6 ) alkenyl or (C 5 -C 6 ) -Cycloalkenyl, (C 3 -C 4 ) alkynyl which is optionally mono- or disubstituted by (C 1 -C 6 ) alkyl, phenyl, halogen or (C 1 -C 2 alkoxy), phenyl which is optionally is substituted one to three times by (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, halogen, N0 2 or CF 3 , furfuryl, tetrahydrofurfuryl or a cation equivalent of an organic or inorganic base,
  • R 4 (C 1 -C 6 ) alkyl, which is optionally substituted by (C 1 -C 4 ) alkoxy, halogen or phenyl, the latter likewise being mono- to triple by (C 1 -C 4 ) alkyl and halogen can be substituted; (C 3 -C 6 ) alkenyl or phenyl, which is optionally mono- to trisubstituted by (C 1 -C 4 ) alkyl and / or halogen,
  • R 5 and R 6 are identical or different and are H, (C 1 -C 6 ) alkyl, hydroxy- (C 1 -C 6 ) alkyl, (C 5 -C 6 ) cycloalkyl or phenyl, which is optionally is substituted three times by (C 1 -C 4 ) alkyl, (C 1 -C 4 ) alkoxy, halogen or CF 3 (with the proviso that R 5 and R 6 are not together phenyl), or together mean one Form a methylene chain with 2, 4 or 5 links, in which a CH 2 group can optionally be replaced by O, NH or N (CH 3 ),
  • R 7 H or CH 3 ,
  • RgH, CH 3 or C 2 H 5 ,
  • R 9 is H, CH 3 , C 2 H 5 or phenyl with the restriction that if R 1 is trifluoromethyl, R 2 is hydrogen and R is a group of the formula II, R 3 is not hydrogen (IT) or with the restriction that that in compounds in which R is the group of the formula II, R 3 can only be H or unsubstituted alkyl if R 1 or R 2 is CI in the para position (BE, DE, FR, GB, NL, SE) .

In der vorliegenden Beschreibung bedeutet Halogen stets Chlor oder Brom.In the present description, halogen always means chlorine or bromine.

Man erhält die genannten Verbindungen, indem man

  • a) entsprechend substituierte Phenole oder Phenolate der allgemeinen Formel
    Figure imgb0005
    in der X ein Alkaliatom oder Wasserstoff bedeutet, mit substituierten L-Propionsäureestern der allgemeinen Formel
    Figure imgb0006
    in der Y Chlor, Brom oder eine Sulfonyloxygruppe bedeutet oder
  • b) falls R einen Rest der Formel III, IV oder V bedeutet, auch Verbindungen der Formel
    Figure imgb0007
    mit einem entsprechend substituierten 2-Halogen-pyridin, -benzthiazol oder -benzoxazol umsetzt, und gewünschtenfalls die erhaltenen Verbindungen der Formel I in andere Verbindungen der Formel I überführt.
The compounds mentioned are obtained by
  • a) appropriately substituted phenols or phenolates of the general formula
    Figure imgb0005
     in which X represents an alkali atom or hydrogen, with substituted L-propionic acid esters of the general formula
    Figure imgb0006
     in which Y is chlorine, bromine or a sulfonyloxy group or
  • b) if R is a radical of the formula III, IV or V, also compounds of the formula
    Figure imgb0007
     with an appropriately substituted 2-halopyridine, benzothiazole or benzoxazole, and, if desired, convert the compounds of the formula I obtained into other compounds of the formula I.

Bei dem erfindungsgemäßen Verfahren nach a) findet eine Waldensche Umkehrung statt, wobei die L-Konfiguration des Propionsäurederivates in die D-Konfiguration des Endproduktes übergeht.

  • a) Zur Durchführung des Verfahrens a) bedient man sich allgemein bekannter Verfahrensbedingungen. Bei Verwendung eines Phenols als Ausgangsmaterial (X = H) arbeitet man bevorzugt in Gegenwart eines Alkalicarbonates als Säurefänger und in einem polaren Lösungsmittel, vorzugsweise Aceton, Methyläthylketon, Acetonitril, Dimethylformamid oder Dimethylsulfoxyd bei Temperaturen zwischen 50 und 150 °C. Verwendet man als Ausgangsverbindung der Formel VII ein Phenolat (X = Alkaliatom, vorzugsweise Na oder K), so empfiehlt sich die Anwendung von hochsiedenden Lösungsmitteln wie Toluol, Xylol, DMF oder DMSO und von Temperaturen von 100-150 °C. Unter der Sulfonyloxygruppe in Y ist die Gruppe R10-SO2O- zu verstehen, in der R10 einen aliphatischen oder aromatischen Rest bedeutet, vorzugsweise der Mesylatrest (CH3SO2O-), der Rest CF3SO2O-, der Benzolsulfonatrest, der Tosylatrest (p-CH3-C6H4-SO2O-) oder ein durch N02 oder OCH3 substituierter Benzolsulfonatrest.
  • b) Die Umsetzung gemäß b) verläuft unter den gleichen Bedingungen wie a). Die Ausgangsverbindungen der Formel IX erhält man aus Hydrochinon-monobenzyläther bzw. dessen Alkalisalzen der Formel
    Figure imgb0008
    durch Umsetzung mit Verbindungen der Formel VIII und hydrogenolytische Abspaltung der Benzylgruppe. Als Katalysatoren eignen sich besonders Edelmetallkatalysatoren wie Palladium/Tierkohle.
In the method according to a) according to the invention, a Waldensian reversal takes place, the L configuration of the propionic acid derivative being converted into the D configuration of the end product.
  • a) To carry out process a), generally known process conditions are used. When using a phenol as the starting material (X = H), it is preferred to work in the presence of an alkali carbonate as an acid scavenger and in a polar solvent, preferably acetone, methyl ethyl ketone, acetonitrile, dimethylformamide or dimethyl sulfoxide at temperatures between 50 and 150 ° C. If a phenolate (X = alkali atom, preferably Na or K) is used as the starting compound of the formula VII, the use of high-boiling solvents such as toluene, xylene, DMF or DMSO and temperatures of 100-150 ° C. is recommended. The sulfonyloxy group in Y is to be understood as the group R 10 -SO 2 O-, in which R 10 is an aliphatic or aromatic residue, preferably the mesylate residue (CH 3 SO 2 O-), the residue CF 3 SO 2 O-, the benzenesulfonate residue, the tosylate residue (p-CH 3 -C 6 H 4 -SO 2 O-) or a through N0 2 or OCH 3 substituted benzenesulfonate.
  • b) The implementation according to b) proceeds under the same conditions as a). The starting compounds of formula IX are obtained from hydroquinone monobenzyl ether or its alkali metal salts of the formula
    Figure imgb0008
     by reaction with compounds of the formula VIII and hydrogenolytic cleavage of the benzyl group. Precious metal catalysts such as palladium / animal charcoal are particularly suitable as catalysts.

Die nach a) oder b) erhaltenen Verbindungen der Formel 1 kann man gewünschtenfalls durch allgemein bekannte Operationen in andere Verbindungen der Formel I überführen. So erhält man aus Estern durch alkalische Verseifung Salze (R3 = Kat), die wiederum in die freien Säuren (R3 = H) überführt werden können. Letztere liefern auf dem Umweg über die Säurehalogenide die entsprechenden Amide, Hydrazide oder Thioester. Durch Veresterung der freien Säuren oder der Säurechloride oder durch direkte Umesterung entstehen andere Ester der Formel I.If desired, the compounds of formula 1 obtained according to a) or b) can be converted into other compounds of formula I by generally known operations. Thus, salts (R 3 = Kat) are obtained from esters by alkaline saponification, which in turn can be converted into the free acids (R 3 = H). The latter supply the corresponding amides, hydrazides or thioesters via the acid halides. By esterifying the free acids or acid chlorides or by direct transesterification, other esters of the formula I are formed.

Bei Verwendung von optisch reinem Ausgangsmaterial liefern die erfindungsgemäßen Verfahren Endprodukte mit einer optischen Reinheit von mindestens 60 % entsprechend einem Anteil von 80 % der D-Form. Wenn gewünscht, kann die optische Reinheit der Verbindungen nach üblichen Verfahren, z.B. Umkristallisation weiter erhöht werden. Falls diese Verbindungen, insbesondere die Ester, flüssig sind, ist es ein bevorzugtes Reinigungsverfahren, die zunächst erhaltenen Ester zur entsprechenden Phenoxypropionsäure zu verseifen, diese in an sich bekannter Weise durch Umkristallisation von etwa vorhandenen geringen Mengen der L-Form zu reinigen und dann aus der weitgehend reinen Säure nach einem der vorstehend angegebenen Verfahren die gewünschten Verbindungen der Formel I herzustellen.When using optically pure starting material, the processes according to the invention deliver end products with an optical purity of at least 60%, corresponding to a proportion of 80% of the D-form. If desired, the optical purity of the compounds can be determined by conventional methods, e.g. Recrystallization can be further increased. If these compounds, in particular the esters, are liquid, it is a preferred cleaning process to saponify the esters initially obtained to the corresponding phenoxypropionic acid, to purify them in a manner known per se by recrystallization of any small amounts of the L-form present and then from the largely pure acid to produce the desired compounds of formula I by one of the methods given above.

Bevorzugte Verbindungen der Formel 1 sind solche, in denen das Paar R1/R2H/CI, H/Br, H/CF3, CI/CF3, CI/CI, CI/Br bzw. (wenn R einen Rest der Formel IV oder V darstellt) auch H/H bedeutet. Bedeutet R einen Rest der Formel II oder VI, so befinden sich die Reste R1 und R2 bevorzugt in 4- oder in 2,4-Stellung, während bei R=Rest der Formel IV oder V die Positionen 5 und 6 besonders bevorzugt sind.Preferred compounds of formula 1 are those in which the pair R 1 / R 2 H / CI, H / Br, H / CF 3 , CI / CF 3 , CI / CI, CI / Br or (if R is a radical of the Formula IV or V) also means H / H. If R is a radical of the formula II or VI, the radicals R 1 and R 2 are preferably in the 4- or in the 2,4-position, while in the case of R = radical of the formula IV or V, positions 5 and 6 are particularly preferred .

Außer den in den Beispielen aufgeführten Verbindungen sind folgende Verbindungen besonders wirksam :

  • D-2-[4-(4-Chlorphenoxy)-phenoxy]-propionsäure
  • D-2-[4-(4-Chlorphenoxy)-phenoxy]-propionsäure-methylester-n-propylester, -isopropylester,
  • D-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäure,
  • Natrium-D-2-[4-(2,4-Dichlorphenoxy) phenoxy]-propionat, Dimethylammonium-D-2-[4-(2,4-Dichlorpheno- xy)-phenoxy]-propionat,
  • D-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäure-isopropylester, -isobutylester, -n-amylester,
  • D-2-[4-(4-Brom-2-chlorphenoxy)-phenoxy]-propionsäure-n-propylester,
  • Kalium-D-2-[4-(4-Brom-2-chlorphenoxy)-phenoxy]-propionat, Diäthylammonium-D-2-[4-(4-Brom-2-chlor- phenoxy)-phenoxy]-propionat,
  • D-2-[4-(4-Brom-2-chlorphenoxy)-phenoxy]-propionsäure-sec-amylester,
  • Ammonium-D-2-[4-(4-Trifluormethylphenoxy)-phenoxy]-propionat,
  • Methylammonium-D-2-[4-(4-Trifluormethylphenoxy) phenoxy]-propionat,
  • D-2-[4-(4-Trifluormethylphenoxy)-phenoxy]-propionsäure-n-propylester, -isobutylester,
  • D-2-[4-(2-Chlor-4-Trifluormethyl-phenoxy)-phenoxy]-propionsäure -methylester, -äthylester, n- und i-propylester, n- und i-butylester, -Na- und K-Salz,
  • D-2-[4-(4-Chlorbenzyl)-phenoxy]-propionsäure,
  • D-2-[4-(2,4-Dichlorbenzyl)-phenoxy]-propionsäure-methylester, -äthylester, -isobutylester,
  • D-2-[4-(2,4-Dichlorbenzylhphenoxy]-propionsäure-propylester, -isoamylester, -äthylester,
  • D-2-[4-(2,4-Dichlorbenzyl)-phenoxy]-propionsäure,
  • Natrium-D-2-[4-(2,4-Dichlorbenzyl)-phenoxy]-propionat, D-2-[4-(3,5-Dichlor-2-pyridyloxy)-phenoxy]-propionsäure, D-2-[4-(3,5-Dichlor-2-pyridyloxy)-phenoxy]-propionsäure-methylester, -äthylester, -propylester, -isopropylester, -isobutylester, -Natriumsalz,
  • D-2-[4-(5-Chlor-2-benzoxazolyloxy)-phenoxy]-propionsäure-methylester, -äthylester, -propylester, -isopropylester, -isobutylester,
  • D-2-[4-(6-Chlor-2-benzoxazolyloxy)-phenoxy]-propionsäure-methylester, -äthylester, -propylester, -isopropylester, -isobutylester,
  • D-2-[4-(6-Chlor-2-benzthiazolyloxy)-phenoxy]-propionsäure-methylester, -äthylester, -propylester, -isopropylester, -isobutylester,
  • D-2-[4-(2-Benzthiazolyloxy)-phenoxy]-propionsäure-methylester, -äthylester,
  • D-2-[4-(2-Benzoxazolyloxy)-phenoxy]-propionsäure-methylester, -äthylester,
  • D-2-[4-(6-Brom-2-benzthiazolyloxy)-phenoxy]-propionsäure-äthylester,
  • D-2-[4-(6-Brom-2-benzoxazoiytoxy)-phenoxy]-propionsäure-äthy!ester.
In addition to the compounds listed in the examples, the following compounds are particularly effective:
  • D-2- [4- (4-chlorophenoxy) phenoxy] propionic acid
  • D-2- [4- (4-chlorophenoxy) phenoxy] propionic acid methyl ester n-propyl ester, isopropyl ester,
  • D-2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid,
  • Sodium D-2- [4- (2,4-dichlorophenoxy) phenoxy] propionate, dimethylammonium D-2- [4- (2,4-dichlorophenoxy) phenoxy] propionate,
  • D-2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid isopropyl ester, isobutyl ester, n-amyl ester,
  • D-2- [4- (4-bromo-2-chlorophenoxy) phenoxy] propionic acid n-propyl ester,
  • Potassium D-2- [4- (4-bromo-2-chlorophenoxy) phenoxy] propionate, diethylammonium D-2- [4- (4-bromo-2-chlorophenoxy) phenoxy] propionate,
  • D-2- [4- (4-bromo-2-chlorophenoxy) phenoxy] propionic acid sec-amyl ester,
  • Ammonium D-2- [4- (4-trifluoromethylphenoxy) phenoxy] propionate,
  • Methylammonium D-2- [4- (4-trifluoromethylphenoxy) phenoxy] propionate,
  • D-2- [4- (4-trifluoromethylphenoxy) phenoxy] propionic acid n-propyl ester, isobutyl ester,
  • D-2- [4- (2-chloro-4-trifluoromethylphenoxy) phenoxy] propionic acid, methyl ester, ethyl ester, n- and i-propyl ester, n- and i-butyl ester, -Na- and K-salt ,
  • D-2- [4- (4-chlorobenzyl) phenoxy] propionic acid,
  • D-2- [4- (2,4-dichlorobenzyl) phenoxy] propionic acid methyl ester, ethyl ester, isobutyl ester,
  • D-2- [4- (2,4-dichlorobenzylhphenoxy] propionic acid propyl ester, isoamyl ester, ethyl ester,
  • D-2- [4- (2,4-dichlorobenzyl) phenoxy] propionic acid,
  • Sodium D-2- [4- (2,4-dichlorobenzyl) phenoxy] propionate, D-2- [4- (3,5-dichloro-2-pyridyloxy) phenoxy] propionic acid, D-2- [4- (3,5-dichloro-2-pyridyloxy) phenoxy] propionic acid methyl ester, ethyl ester, propyl ester, isopropyl ester, isobutyl ester, sodium salt,
  • D-2- [4- (5-chloro-2-benzoxazolyloxy) phenoxy] propionic acid methyl ester, ethyl ester, propyl ester, isopropyl ester, isobutyl ester,
  • D-2- [4- (6-chloro-2-benzoxazolyloxy) phenoxy] propionic acid methyl ester, ethyl ester, propyl ester, isopropyl ester, isobutyl ester,
  • D-2- [4- (6-chloro-2-benzothiazolyloxy) phenoxy] propionic acid methyl ester, ethyl ester, propyl ester, isopropyl ester, isobutyl ester,
  • D-2- [4- (2-benzothiazolyloxy) phenoxy] propionic acid methyl ester, ethyl ester,
  • D-2- [4- (2-benzoxazolyloxy) phenoxy] propionic acid methyl ester, ethyl ester,
  • D-2- [4- (6-bromo-2-benzothiazolyloxy) phenoxy] propionic acid ethyl ester,
  • D-2- [4- (6-bromo-2-benzoxazoiytoxy) phenoxy] propionic acid ethyl ester.

Ferner seien folgende Verbindungen genannt :

  • D-2-[4-(4-Chlorphenoxy) phenoxy]-propionsäure-2-chloräthylester, -2,3-dichlor-n-propylester, -cyclohexylester, -propargyl-, äthylthiolester, -dimethylamid,
  • D-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäure-2-methylaminoäthylester, -allylester, -3,4-dichlor- benzylester, -diäthylamid, -2N-methylhydrazid, -thioamid,
  • D-2-[4-(4-Brom-2-chlorphenoxy)-phenoxy]-propionsäure-2-äthylthioäthylester, -N-n-propylaminoäthylester, -2-chlorallylester, -4-chlorbenzylthiolester, -phenylhydrazid,
  • D-2-[4-(4-Trifluormethyl-phenoxy)-phenoxy]-propionsäure-2-(4-chlorphenyl)-äthylester, -n-octylester, -methylallylester, -(3-phenyl)-propargylester, -n-propylamid,
  • D-2-[4-(2,4-Dichlorbenzyl)-phenoxy]-propionsäure-n-dodecylester, -benzylthioester, -cyclohexylamid, -'N,2N-dimethylhydrazid,
  • D-2-[4-(4-Chlorbenzyl)-phenoxy]-propionsäure-cyclopentylester, -äthoxyäthylamid,
  • D-2-[4-(2-Chlor-4-trifluormethylphenoxy)-phenoxy]-propionsäure-äthylester, -2-methoxyäthylester, -n-hexylester, -cyclohexylester, -amid, -anilid, -p-chloranilid,
  • D-2-[4-(5-Chlor-2-pyridyloxy)-phenoxy]-propionsäure,
  • D-2-[4-(5-Chlor-2-pyridyloxy)-phenoxy]-propionsäure-methylester, -isoamylester, -methoxyäthylester, -3-methoxybutylester, -2-chlorpropylester, -allylester, -propargylester,
  • D-2-[4-(5-Brom-2-pyridyloxy)-phenoxy]-propio nsäu re,
  • D-2-[4-(5-Brom-2-pyridyloxy)-phenoxy]-propionsäure-methylester, -äthylester, -amid, -dimethylamid, - hydrazid, -anilid,
  • D-2-[4-(3,5-Dichlor-2-pyridyloxy)-phenoxy]-propionsäure-isobutylester, -2-chloräthylester, -1-methylpro- pargylester, -cyclohexylester, -cyclohexenylester, -2-chlorcyclohexylester, -butoxyäthylester, -methoxyäthylester, -6-chlorhexylester, -amid, -dimethylamid, -diäthylamid, -anilid, -Kaliumsalz, -Ammoniumsalz, - dimethylammoniumsalz, D-2-[4-(3-Chlor-5-brom-2-pyridyloxy)-phenoxy]-propionsäure,
  • D-2-[4-(3.Chlor-5-brom-2-pyridyloxy)-phenoxy]-propionsäure-methylester, -äthylester,
  • D-2-[4-(3-Brom-5-chlor-2-pyridyloxy)-phenoxy]-propionsäure-isopropylester,
  • D-2-[4-(5-Chlor-3-methyl-2-pyridyloxy)-phenoxy]-propionsäure,
  • D-2-[4-(5-Chlor-3-methyl-2-pyridyloxy)-phenoxy]-propionsäure-methylester, -äthylester,
  • D-2-[4-(2-Benzthiazolyloxy)-phenoxy]-propionsäure-isobutylester, -3-chlorpropylester, -allylester, -1-phe- nylpropargylester, -amid,
  • D-2-[4-(5-Chlor-2-benzthiazolyloxy)-phenoxy]-propionsäure-methylester, -äthylester, -isobutylester,
  • D-2-[4-(6-Chlor-2-benzthiazolyloxy)-phenoxy]-propionsäure-isoamylester, -isooctylester, -2-chloräthylester, -3-chlorpropylester, -1,3-dichlorisopropylester, -6-chlorhexylester, -2-methoxyäthylester, -2-butoxyäthylester, -3-methoxybutylester, -allylester, -cyclohexylester, -1,1-dimethylpropargylester, -cyclohexenylester,
  • D-2-[4-(6-Trifluormethyl-2-benzthiazolyloxy)-phenoxy]-propionsäure-methylester, -äthylester, -propylester, -isopropylester, -isobutylester,
  • D-2-[4-(5-Trifluormethyl-2-benzthiazolyloxy)-phenoxy]-propionsäure-methylester, -äthylester,
  • D-2-[4-(6-Brom-2-benzthiazolyloxy)-phenoxy]-propionsäure-methylester, -propylester, -isobutylester, D-2-(4-(5-Brom-2-benzthiazolyloxy)-phenoxy]-propionsäure-äthylester,
  • D-2-[4-(5-Brom-2-benzoxazolyloxy)-phenoxy]-propionsäure-methylester, -äthylester, -isopropylester, -isobutylester,
  • D-2-[4-(6-Brom-2-benzoxazolyloxy)-phenoxy]-propionsäure-methylester, -propylester, -isobutylester,
  • D-2-[4-(6-Trifluormethyl-2-benzoxazolyloxy)-phenoxy]-propionsäure-methylester, -äthylester, -propylester,
  • D-2-[4-(5-Chlor-2-benzoxazolyloxy)-phenoxy]-propionsäure-isoamylester, -2-chloräthylester, -3-chlorpro- pylester, -2-methoxyäthylester, -3-methoxybutylester, -methoxyäthoxy-äthylester, -cyclohexylester, -allylester, -propargylester,
  • D-2-[4-(6-Chlor-2-benzoxazolyloxy)-phenoxy]-propionsäure-isobutylester, -1,3-dichlorisopropylester, -6- chlorhexylester, -1-methoxyäthylester, -cyclohexylester, -2-chlorcyclohexylester, -1-äthylpropargylester.
The following compounds are also mentioned:
  • D-2- [4- (4-chlorophenoxy) phenoxy] -propionic acid-2-chloroethyl ester, -2,3-dichloro-n-propyl ester, -cyclohexyl ester, -propargyl-, ethylthiolester, -dimethylamide,
  • D-2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid 2-methylaminoethyl ester, -allyl ester, -3,4-dichlorobenzyl ester, -diethylamide, - 2 N-methylhydrazide, -thioamide,
  • D-2- [4- (4-bromo-2-chlorophenoxy) phenoxy] propionic acid 2-ethylthioethyl ester, -Nn-propylaminoethyl ester, -2-chloroallyl ester, -4-chlorobenzylthiol ester, -phenyl hydrazide,
  • D-2- [4- (4-trifluoromethylphenoxy) phenoxy] propionic acid 2- (4-chlorophenyl) ethyl ester, n-octyl ester, methyl allyl ester, - (3-phenyl) propargyl ester, -n- propylamide,
  • D-2- [4- (2,4-dichlorobenzyl) phenoxy] propionic acid n-dodecyl ester, -benzylthioester, -cyclohexylamide, -'N, 2 N-dimethylhydrazide,
  • D-2- [4- (4-chlorobenzyl) phenoxy] propionic acid cyclopentyl ester, ethoxyethyl amide,
  • D-2- [4- (2-chloro-4-trifluoromethylphenoxy) phenoxy] propionic acid ethyl ester, -2-methoxyethyl ester, -n-hexyl ester, -cyclohexyl ester, -amide, -anilide, -p-chloroanilide,
  • D-2- [4- (5-chloro-2-pyridyloxy) phenoxy] propionic acid,
  • D-2- [4- (5-chloro-2-pyridyloxy) phenoxy] propionic acid methyl ester, isoamyl ester, methoxyethyl ester, -3-methoxybutyl ester, -2-chloropropyl ester, allyl ester, propargyl ester,
  • D-2- [4- (5-bromo-2-pyridyloxy) phenoxy] propionic acid,
  • D-2- [4- (5-bromo-2-pyridyloxy) phenoxy] propionic acid methyl ester, ethyl ester, amide, dimethyl amide, hydrazide, anilide,
  • D-2- [4- (3,5-dichloro-2-pyridyloxy) phenoxy] propionic acid isobutyl ester, -2-chloroethyl ester, -1-methylpropargyl ester, -cyclohexyl ester, -cyclohexenyl ester, -2-chlorocyclohexyl ester, - butoxyethyl ester, methoxyethyl ester, 6-chlorohexyl ester, amide, dimethyl amide, diethyl amide, anilide, potassium salt, ammonium salt, dimethyl ammonium salt, D-2- [4- (3-chloro-5-bromo-2-pyridyloxy ) -phenoxy] -propionic acid,
  • D-2- [4- (3rd chloro-5-bromo-2-pyridyloxy) phenoxy] propionic acid methyl ester, ethyl ester,
  • D-2- [4- (3-bromo-5-chloro-2-pyridyloxy) phenoxy] propionic acid isopropyl ester,
  • D-2- [4- (5-chloro-3-methyl-2-pyridyloxy) phenoxy] propionic acid,
  • D-2- [4- (5-chloro-3-methyl-2-pyridyloxy) phenoxy] propionic acid methyl ester, ethyl ester,
  • D-2- [4- (2-benzothiazolyloxy) phenoxy] propionic acid isobutyl ester, -3-chloropropyl ester, allyl ester, -1-phenyl propargyl ester, amide,
  • D- 2 - [4- (5-chloro-2-benzothiazolyloxy) phenoxy] propionic acid methyl ester, ethyl ester, isobutyl ester,
  • D-2- [4- (6-chloro-2-benzothiazolyloxy) phenoxy] propionic acid isoamyl ester, isooctyl ester, -2-chloroethyl ester, -3-chloropropyl ester, -1,3-dichloroisopropyl ester, -6-chlorohexyl ester, - 2-methoxyethyl ester, -2-butoxyethyl ester, -3-methoxybutyl ester, -allyl ester, -cyclohexyl ester, -1,1-dimethylpropargyl ester, -cyclohexenyl ester,
  • D- 2 - [4- (6-trifluoromethyl-2-benzothiazolyloxy) phenoxy] propionic acid, methyl ester, ethyl ester, propyl ester, isopropyl ester, isobutyl ester,
  • D-2- [4- (5-trifluoromethyl-2-benzothiazolyloxy) phenoxy] propionic acid methyl ester, ethyl ester,
  • D-2- [4- (6-bromo-2-benzothiazolyloxy) phenoxy] propionic acid methyl ester, propyl ester, isobutyl ester, D-2- (4- (5-bromo-2-benzothiazolyloxy) phenoxy] - ethyl propionate,
  • D-2- [4- (5-bromo-2-benzoxazolyloxy) phenoxy] propionic acid methyl ester, ethyl ester, isopropyl ester, isobutyl ester,
  • D-2- [4- (6-bromo-2-benzoxazolyloxy) phenoxy] propionic acid methyl ester, propyl ester, isobutyl ester,
  • D-2- [4- (6-trifluoromethyl-2-benzoxazolyloxy) phenoxy] propionic acid methyl ester, ethyl ester, propyl ester,
  • D-2- [4- (5-chloro-2-benzoxazolyloxy) phenoxy] propionic acid isoamyl ester, -2-chloroethyl ester, -3-chloropropyl ester, -2-methoxyethyl ester, -3-methoxybutyl ester, -methoxyethoxy-ethyl ester , -cyclohexyl ester, -allylester, -propargylester,
  • D-2- [4- (6-chloro-2-benzoxazolyloxy) phenoxy] propionic acid isobutyl ester, 1,3-dichloroisopropyl ester, 6-chlorohexyl ester, -1-methoxyethyl ester, cyclohexyl ester, -2-chlorocyclohexyl ester, - 1-ethylpropargylester.

Wie eingangs erwähnt, zeichnen sich die erfindungsgemäßen D-Enantiomeren gegenüber den vorbeschriebenen Racematen durch eine erheblich gesteigerte herbizide Wirkung aus. Überraschenderweise zeigte sich, daß die L-Enantiomeren im Nachauflauf praktisch unwirksam sind. Die Wirksamkeit der Racemate beruht somit praktisch allein auf ihrem Gehalt an D-Enantiomeren.As mentioned at the beginning, the D-enantiomers according to the invention are distinguished from the racemates described above by a considerably increased herbicidal action. Surprisingly, it was found that the L-enantiomers are practically ineffective after emergence. The effectiveness of the racemates is based practically solely on their content of D-enantiomers.

Gegenstand der Erfindung sind somit auch herbizide Mittel, die gekennzeichnet sind durch einen Gehalt an einem Wirkstoff der Formel I, der weniger als 20 Gewichtsprozent, vorzugsweise weniger als 10 Gewichtsprozent, insbesondere weniger als 5 Gewichtsprozent des L-Enantiomeren enthält, in Kombination mit üblichen Hilfs- und Trägerstoffen. Die Formulierung für die praktische Anwendung erfolgt nach denselben Methoden und mit den gleichen Zusatzstoffen wie sie für die Racemate bereits bekannt sind. Bevorzugte Formulierungen sind Flüssigformulierungen oder ULV-Formulierungen. Die Formulierungen enthalten die Wirkstoffe vorzugsweise zu 2-95 % je nach Zubereitungsart. Wegen ihrer besseren Wirksamkeit kann mit den erfindungsgemäßen optisch aktiven Wirkstoffen die erforderliche Aufwandmenge pro Flächeneinheit gegenüber den Racematen um bis zu 60 % reduziert werden ; sie liegt im allgemeinen zwischen 0.01-5 kg/ha, vorzugsweise bei 0.05 bis 3 kg/ha.The invention thus also relates to herbicidal compositions which are characterized by a content of an active compound of the formula I which contains less than 20% by weight, preferably less than 10% by weight, in particular less than 5% by weight, of the L-enantiomer in combination with customary auxiliaries - and carriers. The formulation for practical use follows the same methods and with the same additives as are already known for the racemates. Preferred formulations are liquid formulations or ULV formulations. The formulations preferably contain 2-95% of the active ingredients, depending on the type of preparation. Because of their better effectiveness, the required application rate per unit area compared to the racemates can be reduced by up to 60% with the optically active active substances according to the invention; it is generally between 0.01-5 kg / ha, preferably 0.05 to 3 kg / ha.

HerstellungsbeispieleManufacturing examples Beispiel 1example 1 D-(+)-2[4-(4-Chlorphenoxy)-phenoxy]-propionsäure-äthylesterD - (+) - 2 [4- (4-chlorophenoxy) phenoxy] propionic acid ethyl ester

Figure imgb0009
220,5 g (1,0 Mol) 4-(4-Chlorphenoxy)-phenol werden mit 299,2 g (1,1 Mol) L-(-)-Milchsäureäthylester- tosylat und 158,7 g (1,15 Mol) gepulvertem, wasserfreiem Kaliumcarbonat in 1000 ml Methyläthylketon 56 Stunden zum Sieden unter Rückfluß erhitzt.
Figure imgb0009
 220.5 g (1.0 mol) of 4- (4-chlorophenoxy) phenol are mixed with 299.2 g (1.1 mol) of L - (-) - lactic acid ethyl ester tosylate and 158.7 g (1.15 mol ) powdered, anhydrous potassium carbonate in 1000 ml of methyl ethyl ketone heated to boiling under reflux for 56 hours.

Nach Erkalten wird vom Salzrückstand abfiltriert, das Lösungsmittel abgedampft und der verbleibende Rückstand im Hochvakuum destilliert.After cooling, the salt residue is filtered off, the solvent is evaporated off and the remaining residue is distilled under high vacuum.

Man erhält 310 g (97 % d.Th.) D-(+)-2-[4-(4-Chlorphenoxy)-phenoxy]-propionsäure-äthylester, Sdp. 159 °C/0,05 mbar ö = 6,5° (1 m, Chloroform.This gives 310 g (97% of theory) of D - (+) - 2- [4- (4-chlorophenoxy) phenoxy] propionic acid ethyl ester, b.p. 159 ° C./0.05 mbar ö = 6. 5 ° (1 m, chloroform.

Beispiel 2Example 2 D-(+)-2-[4-(4-Chlorphenoxy)-phenoxy]-propionsäureD - (+) - 2- [4- (4-chlorophenoxy) phenoxy] propionic acid

Figure imgb0010
32,1 g (0,10 Mol) D-(+)-2-[4-(4-Chlorphenoxy)-phenoxy]-propionsäure-äthylester werden in 150 ml Methanol gelöst und unter Rühren mit 125 ml 2n Natronlauge (0,25 Mol) versetzt. Man erhitzt 2 Stunden auf Siedetemperatur, destilliert anschließend den größten Teil des organischen Lösungsmittels ab und fällt nach Erkalten das Produkt durch Zugabe von Salsäure. Nach Absaugen, Waschen mit Wasser und Trocknen erhält man 28,5 g (97 % d.Th.) D-(+)-2-[4-(4-Chlorphenoxy)-phenoxy]-propionsäure, Schmp. 105°-110 °C,
Figure imgb0011
 (0,4 m, Chloroform).
Figure imgb0010
 32.1 g (0.10 mol) of ethyl D - (+) - 2- [4- (4-chlorophenoxy) phenoxy] propionate are dissolved in 150 ml of methanol and stirred with 125 ml of 2N sodium hydroxide solution (0, 25 mol) added. The mixture is heated to boiling temperature for 2 hours, then most of the organic solvent is distilled off and, after cooling, the product is precipitated by adding salsic acid. After suction, washing with water and drying, 28.5 g (97% of theory) of D - (+) - 2- [4- (4-chlorophenoxy) phenoxy] propionic acid, mp. 105 ° -110 ° C,
Figure imgb0011
 (0.4 m, chloroform).

Beispiel 3Example 3 D-(+)-2-[4-(4-Chlorphenoxy)-phenoxy]-propionsäure-isobutylesterD - (+) - 2- [4- (4-chlorophenoxy) phenoxy] propionic acid isobutyl ester

Figure imgb0012
Figure imgb0012

A. Durch UmesterungA. By transesterification

160,3 g (0.5 Mol) D-(+)-2-[4-(4-Chlorphenoxy)-phenoxy]-propionsäure-äthylester werden in 500 ml Isobutylalkohol gelöst. Nach Zugabe von 2 ml konz. Schwefelsäure erhitzt man 8 Stunden zum Sieden, wobei über eine Kolonne das entstehende Äthanol abgenommen wird. Man destilliert anschliessend das Lösungsmittel im Wasserstrahlvakuum weitgehend ab, nimmt den Rückstand in Methylenchlorid auf und wäscht mit Wasser. Nach Abdestillieren des Methylenchlorids destilliert man das Produkt im Hochvakuum.160.3 g (0.5 mol) of D - (+) - 2- [4- (4-chlorophenoxy) phenoxy] propionic acid ethyl ester are dissolved in 500 ml of isobutyl alcohol. After adding 2 ml of conc. Sulfuric acid is heated to boiling for 8 hours, the resulting ethanol being removed via a column. The solvent is then largely distilled off in a water jet vacuum, the residue is taken up in methylene chloride and washed with water. After the methylene chloride has been distilled off, the product is distilled under a high vacuum.

Man erhält 159,0 g (91 % d.Th.) D-(+)-2-[4-(4-Chlorphenoxy)-phenoxy]-propionsäure-isobutylester, Sdp. 169°-173 °C/0,07 mbar,

Figure imgb0013
(1 m, Chloroform).159.0 g (91% of theory) of D - (+) - 2- [4- (4-chlorophenoxy) phenoxy] propionic acid isobutyl ester, b.p. 169 ° -173 ° C./0.07 mbar,
Figure imgb0013
 (1 m, chloroform).

B. Durch VeresterungB. By esterification

29,3 g (0,1 Mol) D-(+)-2-[4-(4-Chlorphenoxy)-phenoxy]-propionsäure werden in 200 ml Isobutylalkohol gelöst. Nach Zugabe von 0,5 ml konz. Schwefelsäure erhitzt man 15 Stunden zum Sieden, wobei über eine Kolonne das entstehende Wasser abgenommen wird.29.3 g (0.1 mol) of D - (+) - 2- [4- (4-chlorophenoxy) phenoxy] propionic acid are dissolved in 200 ml of isobutyl alcohol. After adding 0.5 ml of conc. Sulfuric acid is heated to boiling for 15 hours, the water formed being removed via a column.

Man destilliert anschließend das Lösungsmittel im Wassertrahlvakuum weitgehend ab, nimmt den Rückstand in Methylenchlorid auf und wäscht mit Wasser. Nach Abdampfen des Methylenchlorids destilliert man das Produkt im Hochvakuum.The solvent is then largely distilled off in a water jet vacuum, the residue is taken up in methylene chloride and washed with water. After evaporation of the methylene chloride, the product is distilled in a high vacuum.

Man erhält 30,1 g (86 % d.Th.) D-(+)-2-[4-(4-Chlorphenoxy)-phenoxy]-propionsäure-isobutylester,

Figure imgb0014
Sdp. 167 °C/0,05 mbar, (1 m, Chloroform).30.1 g (86% of theory) of D - (+) - 2- [4- (4-chlorophenoxy) phenoxy] propionic acid isobutyl ester are obtained,
Figure imgb0014
 Bp 167 ° C / 0.05 mbar, (1 m, chloroform).

Beispiel 4Example 4 D-(+)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäure-methylesterD - (+) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid methyl ester

Figure imgb0015
25,5 g (0,10 Mol) 4-(2,4-Dichlorphenoxy)-phenol werden mit 25,8 g (0,10 Mol) L-(-)-Milchsäuremethyl- ester-tosylat und 15,2 g (0,11 Mol) gepulvertem, wasserfreiem Kaliumcarbonat in 150 ml Acetonitril 14 Stunden zum Sieden unter Rückfluß erhitzt.
Figure imgb0015
 25.5 g (0.10 mol) of 4- (2,4-dichlorophenoxy) phenol are mixed with 25.8 g (0.10 mol) of L - (-) - lactic acid methyl ester tosylate and 15.2 g ( 0.11 mol) of powdered, anhydrous potassium carbonate in 150 ml of acetonitrile is heated to boiling under reflux for 14 hours.

Nach Erkalten wird vom Salzrückstand abfiltriert, das Lösungsmittel abgedampft und der verbleibende Rückstand im Hochvakuum destilliert.After cooling, the salt residue is filtered off, the solvent is evaporated off and the remaining residue is distilled under high vacuum.

Man erhält 28,1 g (82 % d.Th.) D-(+)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäuremethylester, Sdp. 167 °C/0,04 mbar, α 20 D = 6,9° (1 m, Chloroform).28.1 g (82% of theory) of D - (+) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid methyl ester are obtained, bp. 167 ° C./0.04 mbar, α 20 D = 6.9 ° (1 m, chloroform).

Beispiel 5Example 5 D-(+)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäure-äthylesterD - (+) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid ethyl ester

Figure imgb0016
Figure imgb0016

A. Man suspendiert 27,7 g (0,10 Mol) trockenes Natrium-4-(2,4-Dichlorphenoxy)-phenolat in 200 ml Xylol und erhitzt die Suspension auf 110°C. Im Laufe einer halben Stunde tropft man 20,6 g (0,105 Mol) L-(-)-Milchsäureäthylester-mesylat zu und erhitzt 4 Stunden zum Sieden unter Rückfluß.A. Suspend 27.7 g (0.10 mol) of dry sodium 4- (2,4-dichlorophenoxy) phenolate in 200 ml of xylene and heat the suspension to 110 ° C. Over the course of half an hour, 20.6 g (0.105 mol) of L - (-) - lactic acid ethyl ester mesylate are added dropwise and the mixture is heated under reflux for 4 hours.

Nach dem Erkalten trennt man vom ausgeschiedenen Salzrückstand, dampft das Lösungsmittel ab und destilliert den verbleibenden Rückstand im Hochvakuum.After cooling, the separated salt residue is separated off, the solvent is evaporated off and the remaining residue is distilled in a high vacuum.

Man erhält 17,0 g (48 % d.Th.) D-(+)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäureäthylester, Sdp. 196 °C/0,07 mbar, α 20 D = 6,5° (1 m, Chloroform).17.0 g (48% of theory) of D - (+) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid ethyl ester are obtained, bp 196 ° C / 0.07 mbar, α 20 D = 6.5 ° (1 m, chloroform).

B. 10,2 g (0,040 Mol) 4-(2,4-Dichlorphenoxy)-phenol werden mit 12,7 g (0,044 Mol) L-(-)-Milchsäure- äthylester-4-methoxybenzolsulfonat und 6,6 g (0,048 Mol) gepulvertem, wasserfreiem Kaliumcarbonat in 70 ml Aceton 80 Stunden zum Sieden unter Rückfluß erhitzt.B. 10.2 g (0.040 mol) of 4- (2,4-dichlorophenoxy) phenol are mixed with 12.7 g (0.044 mol) of L - (-) - lactic acid ethyl ester-4-methoxybenzenesulfonate and 6.6 g ( 0.048 mol) of powdered, anhydrous potassium carbonate in 70 ml of acetone heated to boiling under reflux for 80 hours.

Nach Erkalten wird vom Salzrückstand abfiltriert, das Lösungsmittel abgedampft und der verbleibende Rückstand im Hochvakuum destilliert.After cooling, the salt residue is filtered off, the solvent is evaporated off and the remaining residue is distilled under high vacuum.

Man erhält 11,5 g (81 % d.Th.) D-(+)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäureäthylester, Sdp. 180 °C/0,04 mbar, α 20 D = 6,6° (1 m, Chloroform).11.5 g (81% of theory) of D - (+) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid ethyl ester are obtained, bp 180 ° C / 0.04 mbar, α 20 D = 6.6 ° (1 m, chloroform).

C. 3,0 g (11,6 mMol) 4-(2,4-Dichlorphenoxy)-phenol werden mit 3,5 g (11,6 mMol) L-(-)-Milchsäure- äthylester-4-nitrobenzolsulfonat und 1,8 g (12,7 mMol) gepulvertem, wasserfreiem Kaliumcarbonat in 40 ml Aceton 24 Stunden zum Sieden unter Rückfluß erhitzt.C. 3.0 g (11.6 mmol) of 4- (2,4-dichlorophenoxy) phenol are mixed with 3.5 g (11.6 mmol) of L - (-) - lactic acid ethyl ester-4-nitrobenzenesulfonate and 1 , 8 g (12.7 mmol) of powdered, anhydrous potassium carbonate in 40 ml of acetone heated to boiling under reflux for 24 hours.

Nach Erkalten wird vom Salzrückstand abfiltriert, das Lösungsmittel und der verbleibende Rückstand im Hochvakuum destilliert. Man erhält 3,6 g (87 % d.Th.) D-(+)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäureäthylester, Sdp. 197°C/0,07 mbar, a ö = 4,7° (0,7 m, Chloroform).After cooling, the salt residue is filtered off, the solvent and the remaining residue are distilled under high vacuum. 3.6 g (87% of theory) of D - (+) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid ethyl ester, bp 197 ° C / 0.07 mbar, a ö = 4.7 ° (0.7 m, chloroform).

Beispiel 6AExample 6A D-(+)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäurechloridD - (+) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid chloride

Figure imgb0017
52,3 g (0,160 Mol) D-(+)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäure, erhalten durch Verseifung des nach Beispiel 5 erhaltenen Äthylesters analog Beispiel 2, werden in 200 ml Toluol gelöst. Nach Zugabe von 22,8 g (0,192 Mol) Thionylchlorid erhitzt man 13 Stunden zum Sieden unter Rückfluß.
Figure imgb0017
 52.3 g (0.160 mol) of D - (+) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid, obtained by saponification of the ethyl ester obtained according to Example 5 analogously to Example 2, are dissolved in 200 ml of toluene solved. After the addition of 22.8 g (0.192 mol) of thionyl chloride, the mixture is heated under reflux for 13 hours.

Durch Destillation unter vermindertem Druck destilliert man Lösungsmittel und nicht umgesetztes Thionylchlorid ab. Den Rückstand von 61,3 g nimmt man in 238,7 g Benzol auf und erhält damit eine ca. 18 %ige Lösung des D-(+)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäurechlorids, die direkt für weitere Umsetzungen verwendbar ist.By distillation under reduced pressure, the solvent and unreacted thionyl chloride are distilled off. The residue of 61.3 g is taken up in 238.7 g of benzene and thus an approximately 18% solution of the D - (+) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid chloride is obtained which can be used directly for further implementations.

Beispiel 6 BExample 6 B D-(+)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäure-2-(methoxy)-äthylesterD - (+) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid 2- (methoxy) ethyl ester

Figure imgb0018
85 g der in Beispiel 6 A erhaltenen benzolischen Lösung des D-(+)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäurechlorids (ca. 45 mMol) werden bei Raumtemperatur zu einer Mischung von 3,8 g (50 mMol) Äthylenglykol-monomethyläther mit 5,1 g (50 mMol) Triäthylamin und 50 ml Benzol zugetropft. Man rührt 3 Stunden bei 50 °C nach, kühlt ab und filtriert vom ausgeschiedenen Triäthylammoniumhydrochlorid. Das Fittrat wird mit Wasser gewaschen, das Benzol abgedampft und der Rückstand durch Chromatographieren an Kieselgel gereinigt.
Figure imgb0018
 85 g of the benzene solution of D - (+) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid chloride (approx. 45 mmol) obtained in Example 6 A are mixed at room temperature with a mixture of 3.8 g (50 mmol) of ethylene glycol monomethyl ether with 5.1 g (50 mmol) of triethylamine and 50 ml of benzene were added dropwise. The mixture is stirred for 3 hours at 50 ° C, cooled and filtered from the separated triethylammonium hydrochloride. The fittrate is washed with water, the benzene is evaporated off and the residue is purified by chromatography on silica gel.

Man erhält 15.7 g (91 % d.Th.) D-(+)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäure-2-(methoxy)-äthylester, α 20 D = 2,60 (0,5 m, Chloroform).15.7 g (91% of theory) of D - (+) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid 2- (methoxy) ethyl ester, α 20 D = 2, 6 0 (0.5 m, chloroform).

Beispiel 7Example 7 D-(+)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäure-3-(methoxy)-n-butylesterD - (+) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid 3- (methoxy) n-butyl ester

Figure imgb0019
85 g der in Beispiel 6 A erhaltenen benzolischen Lösung des D-(+)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäurechlorids (ca. 45 mMol) werden bei Raumtemperatur zu einer Mischung von 5,2 g (50 mMol) 3-Methoxy-1-butanol mit 5,1 g (50 mMol) Triäthylamin und 50 ml Benzol getropft. Man rührt 3 Stunden bei 50 °C nach, kühlt ab und filtriert vom ausgeschiedenen Triäthylammonium-hydrochlorid. Das Filtrat wird mit Wasser gewaschen, das Benzol abgedampft und der Rückstand durch Chromatographieren an Kieselgel gereinigt.
Figure imgb0019
 85 g of the benzene solution of D - (+) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid chloride (approx. 45 mmol) obtained in Example 6 A are mixed at room temperature with a mixture of 5.2 3 g (50 mmol) of 3-methoxy-1-butanol were added dropwise with 5.1 g (50 mmol) of triethylamine and 50 ml of benzene. The mixture is stirred for 3 hours at 50 ° C, cooled and filtered from the separated triethylammonium hydrochloride. The filtrate is washed with water, the benzene is evaporated off and the residue is purified by chromatography on silica gel.

Man erhält 14,5 g (78 %) d.Th.) D-(+)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäure-3-(methoxy)-n-butylester, a20 = 3,0° (0,5 m, Chloroform).14.5 g (78% of theory) of D - (+) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid 3- (methoxy) -n-butyl ester, a20 = 3.0 ° (0.5 m, chloroform).

Beispiel 8Example 8 D-(+)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäuretetrahydrofurfurylesterD - (+) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid tetrahydrofurfurylester

Figure imgb0020
85 g der in Beispiel 6 A erhaltenen benzolischen Lösung des D-(+)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäurechlorids (ca. 45 mMol) werden bei Raumtemperatur zu einer Mischung von 5,1 g (50 mMol) Tetrahydrofurfurylalkohol mit 5,1 g (50 mMol) Triäthylamin und 60 ml Benzol getropft. Man rührt 3 Stunden bei 50 °C nach, kühlt ab und filtriert vom ausgeschiedenen Triäthylammonium-hydrochlorid. Das Filtrat wird mit Wasser gewaschen, das Benzol abgedampft und der Rückstand durch Chromatographieren an Kieselgel gereinigt.
Figure imgb0020
 85 g of the benzene solution of D - (+) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid chloride (approx. 45 mmol) obtained in Example 6 A are mixed at room temperature with a mixture of 5.1 Dropped g (50 mmol) of tetrahydrofurfuryl alcohol with 5.1 g (50 mmol) of triethylamine and 60 ml of benzene. The mixture is stirred for 3 hours at 50 ° C, cooled and filtered from the separated triethylammonium hydrochloride. The filtrate is washed with water, the benzene is evaporated off and the residue is purified by chromatography on silica gel.

Man erhält 16,2 g (88 % d.Th.) D-(+)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäure-tetrahydro- furfurylester, α 20 D = 2,7° (0,5 m, Chloroform).16.2 g (88% of theory) of D - (+) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid tetrahydrofuryl ester, α 20 D = 2.7 ° (0.5 m, chloroform).

Beispiel 9Example 9 D-(+)-2-[4-(4-Brom-2-chlor-phenoxy)-phenoxy]-propionsäure-äthylesterD - (+) - 2- [4- (4-bromo-2-chlorophenoxy) phenoxy] propionic acid ethyl ester

Figure imgb0021
15,0 g (0,050 Mol) 4-(4-Brom-2-chlorphenoxy)-phenol werden mit 10,2 g (0,052 Mol) L-(-)-Milchsäure- äthylester-mesylat und 7,6 g (0,055 Mol) gepulvertem, wasserfreiem Kaliumcarbonat in 100 ml Acetonitril 20 Stunden zum Sieden unter Rückfluß erhitzt.
Figure imgb0021
 15.0 g (0.050 mol) of 4- (4-bromo-2-chlorophenoxy) phenol are mixed with 10.2 g (0.052 mol) of L - (-) - lactic acid ethyl ester mesylate and 7.6 g (0.055 mol ) powdered, anhydrous potassium carbonate in 100 ml of acetonitrile heated to boiling under reflux for 20 hours.

Nach Erkalten filtriert man vom ausgeschiedenen Salzrückstand, dampft das Lösungsmittel ab und destilliert den verbleibenden Rückstand im Hochvakuum.After cooling, the salt residue which has separated out is filtered off, the solvent is evaporated off and the remaining residue is distilled under high vacuum.

Man erhält 17,2 g (86 % d.Th.) D-(+)-2-[4-(4-Brom-2-chlorphenoxy)-phenoxy]-propionsäure-äthylester, Sdp. 190°-193°C/0,033 mbar, α 20 D = 4,5° (1 m, Chloroform).17.2 g (86% of theory) of D - (+) - 2- [4- (4-bromo-2-chlorophenoxy) phenoxy] propionic acid, ethyl ester, b.p. 190 ° -193 ° C. / 0.033 mbar, α 20 D = 4.5 ° (1 m, chloroform).

Beispiel 10Example 10 D-(+)-2-[4-(4-Brom-2-chlor-phenoxy)-phenoxy]-propionsäure-methylesterD - (+) - 2- [4- (4-Bromo-2-chlorophenoxy) phenoxy] propionic acid methyl ester

Figure imgb0022
94,2 g (0,236 Mol) D-(+)-2-[4-(4-Brom-2-chlor-phenoxy)-phenoxy]-propionsäureäthylester (vgl. Beispiel 9) werden in 700 ml Methanol gelöst. Man gibt 3 ml konzentrierte Schwefelsäure hinzu und erhitzt 8 Stunden zum Sieden unter Rückfluß. Man destilliert die entstandene Mischung von Methanol und Äthanol unter vermindertem Druck weitgehend ab, setzt erneut 700 ml Methanol hinzu und erhitzt nochmals 8 Stunden zum Sieden. Anschließend destilliert man das Methanol ab, nimmt den Rückstand in Chloroform auf, wäscht mit Wasser säurefrei und entfernt das Lösungsmittel durch Abdestillieren. Der verbleibende Rückstand wird im Hochvakuum fraktioniert.
Figure imgb0022
 94.2 g (0.236 mol) of D - (+) - 2- [4- (4-bromo-2-chlorophenoxy) phenoxy] propionic acid ethyl ester (cf. Example 9) are dissolved in 700 ml of methanol. 3 ml of concentrated sulfuric acid are added and the mixture is heated under reflux for 8 hours. The resulting mixture of methanol and ethanol is largely distilled off under reduced pressure, 700 ml of methanol are again added and the mixture is heated to boiling for another 8 hours. The methanol is then distilled off, the residue is taken up in chloroform, washed acid-free with water and the solvent is removed by distillation. The remaining residue is fractionated in a high vacuum.

Man erhält als Hauptfraktion 78,6 g (86 % d.Th.) D-(+)-2-[4-(4-Brom-2-chlor-phenoxy)-phenoxyj-pro- pionsäuremethylester, Sdp. 175°-177°C/0,04 mbar, α 20 D = 6,7° (1 m, Chloroform).The main fraction obtained is 78.6 g (86% of theory) of D - (+) - 2- [4- (4-bromo-2-chlorophenoxy) phenoxyj-propionic acid methyl ester, bp 175 ° - 177 ° C / 0.04 mbar, α 20 D = 6.7 ° (1 m, chloroform).

Das Produkt erstarrt beim Erkalten, Fp. 51°-54 °C. Durch Umkristallisieren aus Methanol erhält man die reine Verbindung vom Fp. 56 °C, α 20 D = 8,9° (1 m, Chloroform).The product solidifies on cooling, mp. 51 ° -54 ° C. The pure compound of mp 56 ° C., α 20 D = 8.9 ° (1 m, chloroform) is obtained by recrystallization from methanol.

Beispiel 11Example 11 D-(+)-2-[4-(4-Trifluormethylphenoxy)-phenoxy]-propionsäure-methylesterD - (+) - 2- [4- (4-Trifluoromethylphenoxy) phenoxy] propionic acid methyl ester

Figure imgb0023
25,4 g (0,10 Mol) 4-(4-Trifluormethylphenoxy) phenol werden mit 28,4 g (0,11 Mol) L-(-)-Milchsäure- methylester-tosylat und 16.6 g (0,12 Mol) gepulvertem, wasserfreiem Kaliumcarbonat in 150 ml Acetonitril 15 Stunden zum Sieden unter Rückfluß erhitzt. Nach Erkalten filtriert man vom ausgeschiedenen Salzrückstand, dampft das Lösungsmittel ab und destilliert den verbleibenden Rückstand im Hochvakuum.
Figure imgb0023
 25.4 g (0.10 mol) of 4- (4-trifluoromethylphenoxy) phenol are mixed with 28.4 g (0.11 mol) of L - (-) - lactic acid methyl ester tosylate and 16.6 g (0.12 mol) powdered, anhydrous potassium carbonate in 150 ml of acetonitrile heated to boiling under reflux for 15 hours. After cooling, the salt residue which has separated out is filtered off, the solvent is evaporated off and the remaining residue is distilled under high vacuum.

Man erhält 30,6 g (90 % d.Th.) D-(+)-2-[4-(4-Trifluormethyl-phenoxy)-phenoxy]-propionsäure-methylester, Sdp. 157°-159°C/0,05 mbar, α 20 D = 7,0° (1 m, Chloroform).30.6 g (90% of theory) of D - (+) - 2- [4- (4-trifluoromethylphenoxy) phenoxy] propionic acid methyl ester, b.p. 157 ° -159 ° C / 0 , 05 mbar, α 20 D = 7.0 ° (1 m, chloroform).

Beispiel 12Example 12 D-(+)-2-[4-(4-Trifluormethylphenoxy)-phenoxy]-propionsäure-äthylesterD - (+) - 2- [4- (4-Trifluoromethylphenoxy) phenoxy] propionic acid ethyl ester

Figure imgb0024
152,4 g (0,6 Mol) 4-(4-Trifluormethylphenoxy)-phenol werden mit 179,5 g (0,66 Mol) L-(-)-Milchsäure- äthylester-tosylat und 95,2 g (0,69 Mol) gepulvertem, wassertreiem Kaliumcarbonat in 1 000 ml Aceton 72 Stunden zum Sieden unter Rückfluß erhitzt. Nach Erkalten filtriert man vom ausgeschiedenen Salzrückstand, dampft das Lösungsmittel ab und destilliert den verbleibenden Rückstand im Hochvakuum.
Figure imgb0024
 152.4 g (0.6 mol) of 4- (4-trifluoromethylphenoxy) phenol are mixed with 179.5 g (0.66 mol) of L - (-) - lactic acid ethyl ester tosylate and 95.2 g (0, 69 mol) of powdered, water-free potassium carbonate in 1,000 ml of acetone heated to boiling under reflux for 72 hours. After cooling, filter out the excreted Salt residue, the solvent evaporates and the remaining residue is distilled under high vacuum.

Man erhält 206 g (97% d.Th.) D-(+)-2-[4-(4-Trifluormethylphenoxy)-phenoxy]-propionsäure-äthylester, Sdp. 150°-156°C/0,07 mbar, α 20 D = 5,0° (1 m, Chloroform).206 g (97% of theory) of D - (+) - 2- [4- (4-trifluoromethylphenoxy) phenoxy] propionic acid, ethyl ester, b.p. 150 ° -156 ° C./0.07 mbar, α 20 D = 5.0 ° (1 m, chloroform).

Das Produkt erstarrt beim Erkalten, Fp. 58°-64 °C. Durch Umkristallisieren aus Äthanol erhält man die reine Verbindung vom Fp. 68,5 °C, α 20 D = 9,3° (1 m, Chloroform).The product solidifies on cooling, mp. 58 ° -64 ° C. The pure compound of mp 68.5 ° C., α 20 D = 9.3 ° (1 m, chloroform) is obtained by recrystallization from ethanol.

Beispiel 13Example 13 D-(+)-2-[4-(2,4-Dichlorbenzyl)-phenoxy]-propionsäureäthylesterD - (+) - 2- [4- (2,4-dichlorobenzyl) phenoxy] propionic acid ethyl ester

Figure imgb0025
38,0 g (0,150 Mol) 4-(2,4-Dichlorbenzyl)-phenol werden mit 44,9 g (0,165 Mol) L-(-)-Milchsäureäthylester- tosylat und 28,4 g (0,180 Mol) gepulvertem, wasserfreiem Kaliumcarbonat in 200 ml Acetonitril 22 Stunden zum Sieden unter Rückfluß erhitzt.
Figure imgb0025
 38.0 g (0.150 mol) of 4- (2,4-dichlorobenzyl) phenol are mixed with 44.9 g (0.165 mol) of L - (-) - lactic acid ethyl ester tosylate and 28.4 g (0.180 mol) of powdered, anhydrous Potassium carbonate in 200 ml of acetonitrile heated to boiling under reflux for 22 hours.

Nach Erkalten wird vom Salzrückstand abfiltriert, das Lösungsmittel abgedampft und der verbleibende Rückstand im Hochvakuum destilliert.After cooling, the salt residue is filtered off, the solvent is evaporated off and the remaining residue is distilled under high vacuum.

Man erhält 36,7 g (69 % d.Th.) D-(+)-2-[4-(2,4-Dichlorbenzyl)-phenoxy]-propionsäureäthylester, Sdp. 160°C/0,08 mbar, α 20 D = 7,0° (1 m, Chloroform).This gives 36.7 g (69% of theory) of D - (+) - 2- [4- (2,4-dichlorobenzyl) phenoxy] propionic acid ethyl ester, b.p. 160 ° C / 0.08 mbar, α 20 D = 7.0 ° (1 m, chloroform).

Beispiel 14Example 14 D-(+)-2-[4-(2,4-Dichlorbenzyl)-phenoxy]-propionsäure-methylesterD - (+) - 2- [4- (2,4-dichlorobenzyl) phenoxy] propionic acid methyl ester

Figure imgb0026
22,8 g (0,062 Mol) D-(+)-2-[4-(2,4-Dichlorbenzoyl)-phenoxy]-propionsäureäthylester (vgl. Beispiel 13) werden in 1 600 ml Methanol gelöst. Man gibt 3 ml konzentrierte Schwefelsäure hinzu und erhitzt 30 Stunden zum Sieden unter Rückfluß. Anschließend destilliert man das Methanol ab, nimmt den Rückstand in Chloroform auf, wäscht mit Wasser säurefrei und entfernt das Lösungsmittel durch Abdestillieren.
Figure imgb0026
 22.8 g (0.062 mol) of D - (+) - 2- [4- (2,4-dichlorobenzoyl) phenoxy] propionic acid ethyl ester (cf. Example 13) are dissolved in 1,600 ml of methanol. 3 ml of concentrated sulfuric acid are added and the mixture is refluxed for 30 hours. The methanol is then distilled off, the residue is taken up in chloroform, washed acid-free with water and the solvent is removed by distillation.

Der verbleibende Rückstand wird im Hochvakuum fraktioniert.The remaining residue is fractionated in a high vacuum.

Man erhält 19,9 g (90 % d.Th.) D-(+)-2-[4-(2,4-Dichlorbenzyl)-phenoxy]-propionsäuremethylester, Sdp. 180°C/0,02 mbar, α 20 D = 7,6° (1 m, Chloroform).19.9 g (90% of theory) of D - (+) - 2- [4- (2,4-dichlorobenzyl) phenoxy] propionic acid methyl ester are obtained, bp 180 ° C./0.02 mbar, α 20 D = 7.6 ° (1 m, chloroform).

Beispiel 15Example 15 D-(+)-2-[4-(5-Chlor-2-benzoxazolyloxy)-phenoxy]-propionsäure-äthylesterD - (+) - 2- [4- (5-chloro-2-benzoxazolyloxy) phenoxy] propionic acid ethyl ester

Figure imgb0027
26,2 g (0,1 Mol) 4-(5-Chlor-2-benzoxazolyloxy)-phenol werden mit 16,6 g (0,12 Mol) Kaliumcarbonat in 120 ml Acetonitril 1 1/2 Stunden zum Sieden erhitzt, anschließend werden 29,9 g (0,11 Mol) L-(-)-Milchsäureäthylester-tosylat, gelöst in 50 ml Acetonitril innerhalb von 15 Minuten zugetropft. Das Reaktionsgemisch wird nach der Zugabe 12 Stunden am Sieden gehalten, der Salzanteil wird abfiltriert und vom Filtrat Acetonitril abdestilliert. Der verbleibende Rückstand wird in 200 ml Methylenchlorid aufgenommen, zweimal mit je 200 ml Wasser gewaschen, nach Trocknen über Natriumsulfat wird Methylenchlorid abdestilliert. Der erhaltene Rückstand wird destilliert. Nach der Destillation erhält man 29,8 g (82,5 % d.Th.) an überwiegend D-(+) enthaltendem 2-[4-(5-Chlor-2-benzoxyzolyloxy)-phenoxy]-propionsäureäthylester mit Fp. 53°-55°C und α 20 D = 11,3° (1 m, Chloroform).
Figure imgb0027
 26.2 g (0.1 mol) of 4- (5-chloro-2-benzoxazolyloxy) phenol are heated to boiling with 16.6 g (0.12 mol) of potassium carbonate in 120 ml of acetonitrile, then 29.9 g (0.11 mol) of L - (-) - lactic acid ethyl ester tosylate, dissolved in 50 ml of acetonitrile, are added dropwise within 15 minutes. After the addition, the reaction mixture is kept at the boil for 12 hours, the salt fraction is filtered off and the acetonitrile is distilled off from the filtrate. The remaining residue is taken up in 200 ml of methylene chloride, washed twice with 200 ml of water each time, after drying over sodium sulfate, methylene chloride is distilled off. The residue obtained is distilled. After distillation, 29.8 g (82.5% of theory) of ethyl 2- [4- (5-chloro-2-benzoxyzolyloxy) phenoxy] propionate containing predominantly D - (+) and mp 53 are obtained ° -55 ° C and α 20 D = 11.3 ° (1 m, chloroform).

Beispiel 16Example 16 D-(+)-2-[4-(6-Chlor-2-benzthiazolyloxy)-phenoxy]-propionsäure-äthylesterD - (+) - 2- [4- (6-chloro-2-benzothiazolyloxy) phenoxy] propionic acid ethyl ester

Figure imgb0028
27,8 g (0,1 Mol) 4-(6-Chlor-2-benzthiazolyloxy)-phenol werden mit 16,6 g (0,12 Mol) Kaliumcarbonat in 120 ml Acetonitril 1 1/2 Stunden zum Sieden erhitzt. Anschließend werden 29,9 g (0,11 Mol) L-(-)-Milchsäureäthylester-tosylat, gelöst in 50 ml Acetonitril, innerhalb von 15 Minuten zugetropft. Das Reaktionsgemisch wird nach der Zugabe 5 Stunden am Sieden gehalten, der Salzanteil wird abfiltriert und vom Filtrat Acetonitril Abdestilliert. Der verbleibende Rückstand wird in 200 ml Methylenchlorid aufgenommen, zweimal mit je 100 ml Wasser gewaschen, nach Trocknen über Natriumsulfat wird Methylenchlorid abdestilliert. Der erhaltene Rückstand wird destilliert.
Figure imgb0028
 27.8 g (0.1 mol) of 4- (6-chloro-2-benzothiazolyloxy) phenol are heated to boiling with 16.6 g (0.12 mol) of potassium carbonate in 120 ml of acetonitrile for 1 1/2 hours. Then 29.9 g (0.11 mol) of L - (-) - lactic acid ethyl ester tosylate, dissolved in 50 ml of acetonitrile, are added dropwise over the course of 15 minutes. After the addition, the reaction mixture is kept at the boil for 5 hours, the salt fraction is filtered off and the acetonitrile is distilled off from the filtrate. The remaining residue is taken up in 200 ml of methylene chloride, washed twice with 100 ml of water, after drying over sodium sulfate, methylene chloride is distilled off. The residue obtained is distilled.

Nach der Destillation erhält man 34,5 g (91,4 % d.Th.) an überwiegend D-(+) enthaltenden 2-[4-(6-Chlor-2-benzthiazolyloxy)-phenoxy]-propionsäureäthylester mit Fp. 49 °C und a 20 = 9,5° (1 m, Chloroform).After distillation, 34.5 g (91.4% of theory) of ethyl 2- [4- (6-chloro-2-benzothiazolyloxy) phenoxy] propionate containing predominantly D - (+) are obtained with mp 49 ° C and a 20 = 9.5 ° (1 m, chloroform).

Nach Umkristallisieren aus einem Äthanol/Wasser-Gemisch wird das Produkt optisch reiner und hat dann Fp. 51 °C und α 20 D = 11° (1 m, Chloroform).After recrystallization from an ethanol / water mixture, the product becomes optically cleaner and then has mp. 51 ° C. and α 20 D = 11 ° (1 m, chloroform).

Beispiel 17Example 17 D-(+)-2-[4-(3,5-Dichlor-2-pyridyloxy)-phenoxy]-propionsäure-äthylesterD - (+) - 2- [4- (3,5-dichloro-2-pyridyloxy) phenoxy] propionic acid ethyl ester

Figure imgb0029
19,7 g (0,077 Mol) 4-(3,5-Dichlor-2-pyridyloxy)-phenol werden mit 12,7 g (0,092 Mol) Kaliumcarbonat (wasserfrei) in 150 ml Acetonitril zum Sieden erhitzt. Anschließend tropft man innerhalb von 5 Minuten 23 g (0,085 Mol) L-(-)-Milchsäureäthylester-tosylat, gelöst in 50 ml Acetonitril, zu. Nach der Zugabe wird das Reaktionsgemisch 18 Stunden unter sieden gehalten. Man kühlt ab, saugt vom Salzanteil ab und destilliert vom Filtrat Acetonitril ab. Der verbleibende ölige Rückstand wird in 200 ml Toluol aufgenommen und zweimal mit je 100 ml Wasser gewaschen. Nach Trocknen über Natriumsulfat wird Toluol abdestilliert und der verbleibende Rückstand destilliert.
Figure imgb0029
 19.7 g (0.077 mol) of 4- (3,5-dichloro-2-pyridyloxy) phenol are heated to boiling with 12.7 g (0.092 mol) of potassium carbonate (anhydrous) in 150 ml of acetonitrile. 23 g (0.085 mol) of L - (-) - lactic acid ethyl ester tosylate, dissolved in 50 ml of acetonitrile, are then added dropwise in the course of 5 minutes. After the addition, the reaction mixture is kept at boiling for 18 hours. The mixture is cooled, the salt content is filtered off and the filtrate is distilled off from acetonitrile. The remaining oily residue is taken up in 200 ml of toluene and washed twice with 100 ml of water. After drying over sodium sulfate, toluene is distilled off and the remaining residue is distilled.

Nach der Destillation erhält man 24,8 g (90,4 % d.Th.) D-(+)-2-[4-(3,5-Dichlor-2-pyridyloxy)-phenoxy]-propionsäure-äthylester mit Sdp0.01 : 174°-176 °C/0,013 mbar und α 20 D = 9,7° (1 m, Chloroform).After distillation, 24.8 g (90.4% of theory) of D - (+) - 2- [4- (3,5-dichloro-2-pyridyloxy) phenoxy] propionic acid ethyl ester with bp 0.01 : 174 ° -176 ° C / 0.013 mbar and α 20 D = 9.7 ° (1 m, chloroform).

Beispiel 18Example 18 D-(+)-N,N-Di-n-propylammonium-2-[4-(4-chlorphenoxy)-phenoxy]-propionatD - (+) - N, N-Di-n-propylammonium 2- [4- (4-chlorophenoxy) phenoxy] propionate

Figure imgb0030
13,2 g (45 mMol) der Säure aus Beispiel 4 werden unter Erwärmen in Toluol gelöst. Bei ca. 30 °C gibt man unter Rühren 4,5 g (45 mMol) Di-n-propylamin zu. Nach kurzem Nachrühren saugt man den entstandenen Niederschlag ab und erhält nach Trocknen 17,0 g des Salzes mit einem Fp. von 125-125,5°C, [α]20 + 20,4° (Chloroform).
Figure imgb0030
 13.2 g (45 mmol) of the acid from Example 4 are dissolved in toluene with heating. At about 30 ° C., 4.5 g (45 mmol) of di-n-propylamine are added with stirring. After stirring briefly, the resulting precipitate is filtered off and, after drying, 17.0 g of the salt with an mp of 125-125.5 ° C., [α] 20 + 20.4 ° (chloroform) are obtained.

Beispiel 19Example 19 D-(-)-Natrium-2-[4-(2-chlor-4-trifluormethyl-phenoxy)-phenoxy]-propionatD - (-) - Sodium 2- [4- (2-chloro-4-trifluoromethylphenoxy) phenoxy] propionate

Figure imgb0031
16,2 g (45 mMol) der Säure aus Beispiel 28 werden unter Erwärmen in 100 ml Ethanol gelöst. Man gibt eine Lösung von 1,8 g (45 mMol) Natriumhydroxid in Wasser hinzu und dampft die Lösungsmittel - zuletzt unter vermindertem Druck - ab. Es verbleiben 17,1 g des Natriumsälzes vom Fp. 78-81 °C, [α]D-18,9°.
Figure imgb0031
 16.2 g (45 mmol) of the acid from Example 28 are dissolved in 100 ml of ethanol with heating. A solution of 1.8 g (45 mmol) of sodium hydroxide in water is added and the solvents are evaporated off, finally under reduced pressure. There remain 17.1 g of the sodium salt of mp. 78-81 ° C, [α] D -18.9 °.

Beispiel 20Example 20 D-(+)-Ethyl-2-[4-(6-Chlor-2-benzoxazolyloxy)-phenoxy]-propionatD - (+) - ethyl 2- [4- (6-chloro-2-benzoxazolyloxy) phenoxy] propionate

31,5 g (0,15 Mol) (D+)-Ethyl-2-(4-hydroxyphenoxy)-propionat [α]D 20-37,4° (1n CHCl3) werden mit 24,9 g (0,18 Mol) Kaliumcarbonat in 200 ml Acetonitril 1 Stunde zum Sieden erhitzt. Anschließend werden während 45 min 28,2 g (0,15 Mol) 2,6-Dichlorbenzoxazol gelöst in 80 ml Acetonitril zugetropft. Nach 1 Stunde Reaktionszeit werden 0,85 g 2,6-Dichlorbenzoxazol nachgegeben. 1/2 Stunde nach der Zugabe zeigt das Dünnschichtchromatogramm vollständigen Umsatz an. Das Reaktionsgemisch wird abgekühlt und bei 30 °C zur Entfernung des ausgefallenen Salzes abfiltriert, das Filtrat wird eingeengt und bei 80 °C in Vakuum getrocknet. Es hinterbleiben 54,2 g eines ockerfarbenen Feststoffs, der anschließend zweimal unter Zusatz von Tierkohle aus n-Hexan umkristallisiert wird. Man erhält 37,4 g (D+)-Ethyl-2-[4-(6-chlor-2-benzoxazolyloxy)-phenoxy]-propionat vom Fp. 78,5°C, der Drehwinkel beträgt [α]D 25: 30° (1 n CHCI3).

Figure imgb0032
31.5 g (0.15 mol) of (D +) - ethyl 2- (4-hydroxyphenoxy) propionate [α] D 20 -37.4 ° (1N CHCl 3 ) are mixed with 24.9 g (0.18 Mol) potassium carbonate in 200 ml of acetonitrile heated to boiling for 1 hour. 28.2 g (0.15 mol) of 2,6-dichlorobenzoxazole dissolved in 80 ml of acetonitrile are then added dropwise over 45 minutes. After a reaction time of 1 hour, 0.85 g of 2,6-dichlorobenzoxazole are added. 1/2 hour after the addition, the thin layer chromatogram shows complete conversion. The reaction mixture is cooled and filtered off at 30 ° C. to remove the precipitated salt, the filtrate is concentrated and dried at 80 ° C. in vacuo. 54.2 g of an ocher-colored solid remain, which is then recrystallized twice from n-hexane with the addition of animal charcoal. This gives 37.4 g (D +) - ethyl-2- [4- (6-chloro-2-benzoxazolyloxy) phenoxy] propionate, mp 78.5 ° C, the rotation angle [α] D 25: 30th ° (1 n CHCI 3 ).
Figure imgb0032

Beispiel 21Example 21 D-(+)-2-[4-(2-Nitro-4-trifluormethyl)-phenoxy]-propionsäure-ethylesterD - (+) - 2- [4- (2-Nitro-4-trifluoromethyl) phenoxy] propionic acid ethyl ester

Figure imgb0033
11,3 g (50 mMol) 3-Nitro-4-chlorbenzotrifluorid werden zusammen mit 10,5 g (50 mMol) D-2(4-Hydroxy- phenoxy) propionsäureäthylester und 8,3 g (60 mMol) trockenem, gepulvertem Kaliumcarbonat in 100 ml Acetonitril 7,5 Stunden zum Sieden unter Rückfluß erhitzt. Man filtriert vom Salzgemisch ab und entfernt das Lösungsmittel im Vakuum. Man erhält 20,3 g D-(+)-2-[4-(2-Nitro-4-trifluormethyl-phenoxy)-phenoxy]-propionsäuremethylester, der zur weiteren Reinigung aus Ethanol umkristallisiert werden kann. Das umkristallisierte Produkt schmilzt bei 85-87 °C, [α]D = + 21,7°.
Figure imgb0033
 11.3 g (50 mmol) of 3-nitro-4-chlorobenzotrifluoride together with 10.5 g (50 mmol) of D-2 (4-hydroxyphenoxy) propionic acid ethyl ester and 8.3 g (60 mmol) of dry, powdered potassium carbonate heated to boiling under reflux in 100 ml of acetonitrile for 7.5 hours. The salt mixture is filtered off and the solvent is removed in vacuo. 20.3 g of D - (+) - 2- [4- (2-nitro-4-trifluoromethylphenoxy) phenoxy] propionic acid methyl ester are obtained, which can be recrystallized from ethanol for further purification. The recrystallized product melts at 85-87 ° C, [α] D = + 21.7 °.

Beispiel 22Example 22 D-(-)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-n-propanolD - (-) - 2- [4- (2,4-dichlorophenoxy) phenoxy] n-propanol

Figure imgb0034
Eine Lösung von 35,5 g (0,10 Mol) D-(+)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäure-ethylester (s. Beispiel 20) in 40 ml Tetrahydrofuran tropft man in einer Stunde zu einer unter Rückfluß siedenden Suspension von 5,7 g (0,15 Mol) Lithiumaluminiumhydrid in 70 ml Tetrahydrofuran. Nach weiteren 1,5 Stunden Sieden unter Rückfluß kühlt man ab, gibt langsam 20 ml Ethylacetat zu sowie anschließend 100 ml verdünnte Schwefelsäure. Man trennt die organische Phase ab, extrahiert die wäßrige Phase noch zweimal mit je 50 ml Tetrahydrofuran und engt die vereinigten Tetrahydrofuran-Phasen ein. Der Rückstand wird in Chloroform aufgenommen, dieses mit Wasser gewaschen und getrocknet. Beim Abdampfen des Lösungsmittels verbleiben 30,0 g rohes D-(-)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-n-propanol. Das Produkt kann durch Säulenchromatographie gereinigt werden. n20 D 1,5795, [a]D-18,3°.
Figure imgb0034
 A solution of 35.5 g (0.10 mol) of D - (+) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid ethyl ester (see Example 20) in 40 ml of tetrahydrofuran is added dropwise in one hour to a refluxing suspension of 5.7 g (0.15 mol) of lithium aluminum hydride in 70 ml of tetrahydrofuran. After boiling under reflux for a further 1.5 hours, the mixture is cooled, 20 ml of ethyl acetate are slowly added and then 100 ml of dilute sulfuric acid. The organic phase is separated off, the aqueous phase is extracted twice with 50 ml of tetrahydrofuran each time and the combined tetrahydrofuran phases are concentrated. The residue is taken up in chloroform, washed with water and dried. Evaporation of the solvent leaves 30.0 g of crude D - (-) - 2- [4- (2,4-dichlorophenoxy) phenoxy] n-propanol. The product can be purified by column chromatography. n 20 D 1.5795, [a] D -18.3 °.

Beispiel 23Example 23 D-(-)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäure-N,N-diethylamidD - (-) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid-N, N-diethylamide

Zu einer Lösung von 7,2 g (99 mMol) Diethylamin in 20 ml Toluol tropft man im Laufe einer Stunde eine Lösung von 15,5 g (45 mMol) D-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäurechlorid (vgl. Beispiel 21). Vom entstandenen Amin-Hydrochlorid-Niederschlag wird abgesaugt, das Filtrat mit verd. Salzsäure und Wasser gewaschen. Nach Trocknen und Abdampfen des Lösungsmittels verbleiben 15,1 g öliges D-(-)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäure-N,N-diethylamid, n20 D 1,565 2, [α]D-1,7°.A solution of 15.5 g (45 mmol) of D-2- [4- (2,4-dichlorophenoxy) phenoxy is added dropwise to a solution of 7.2 g (99 mmol) of diethylamine in 20 ml of toluene over the course of an hour ] -propionic acid chloride (see Example 21). The resulting amine hydrochloride precipitate is filtered off, the filtrate is washed with dil. Hydrochloric acid and water. After drying and evaporation of the solvent, 15.1 g of oily D - (-) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid-N, N-diethylamide, n 20 D 1.565 2, [α ] D -1.7 °.

Beispiel 24Example 24 D-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionitrilD-2- [4- (2,4-dichlorophenoxy) phenoxy] propionitrile

Figure imgb0035
14,8 g (45 mMol) D-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionamid (Beispiel 61) werden in 50 ml Toluol gelöst und mit 50 ml (0,68 Mol) Thionylchlorid versetzt. Man erhitzt 16,5 Stunden zum Sieden unter Rückfluß und destilliert anschliessend das Toluol sowie das nicht umgesetzte Thionylchlorid - zuletzt unter vermindertem Druck - ab. Der dunkle Rückstand wird in Chloroform aufgenommen, mit Natriumbicarbonatlösung und Wasser gewaschen und getrocknet. Nach Abdampfen verbleiben 14,9 g rohes D-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionitril, das säulenchromatographisch gereinigt werden kann ; dabei werden 10,2 g (73 % d.Th.) Produkt mit n20 D 1,571 0 erhalten.
Figure imgb0035
 14.8 g (45 mmol) of D-2- [4- (2,4-dichlorophenoxy) phenoxy] propionamide (Example 61) are dissolved in 50 ml of toluene and 50 ml (0.68 mol) of thionyl chloride are added. The mixture is heated to boiling under reflux for 16.5 hours and then the toluene and the unreacted thionyl chloride are distilled - last under reduced pressure - from. The dark residue is taken up in chloroform, washed with sodium bicarbonate solution and water and dried. After evaporation, 14.9 g of crude D-2- [4- (2,4-dichlorophenoxy) phenoxy] propionitrile remain, which can be purified by column chromatography; 10.2 g (73% of theory) of product with n 20 D 1.571 0 are obtained.

Beispiel 25Example 25 D-(-)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäurethioamidD - (-) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid thioamide

Figure imgb0036
13,0 g (40 mMol) D-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionamid (Beispiel 61) werden in 150 ml Acetonitril mit 5,1 g (50 mMol) Triethylamin und 17,8 g (40 mMol) P4S10 23 Stunden bei Raumtemperatur gerührt. Man filtriert vom ausgeschiedenen Feststoff ab, dampft unter vermindertem Druck das Lösungsmittel ab und nimmt den verbliebenen Rückstand in Chloroform auf. Eventuell nicht gelöste Anteile werden abgetrennt. Die Chloroformphase wird anschließend mit verdünnter Salzsäure, Natronlauge und Wasser gewaschen, getrocknet und abgedampft. Es verbleiben 10,3 g (75 % d.Th.) rohes D-(-)-2-[4-(2,4-Dichlorphenoxy)-phenoxy]-propionsäurethioamid. Nach Umkristallisieren aus Ethanol erhält man hellgelbe Kristalle vom Fp. 153-153,5 °C, [α]D - 15,4°.
Figure imgb0036
 13.0 g (40 mmol) of D-2- [4- (2,4-dichlorophenoxy) phenoxy] propionamide (Example 61) are dissolved in 150 ml of acetonitrile with 5.1 g (50 mmol) of triethylamine and 17.8 g (40 mmol) of P 4 S 10 stirred for 23 hours at room temperature. The solid which has separated out is filtered off, the solvent is evaporated off under reduced pressure and the residue which remains is taken up in chloroform. Any unresolved portions are separated. The chloroform phase is then washed with dilute hydrochloric acid, sodium hydroxide solution and water, dried and evaporated. There remain 10.3 g (75% of theory) of crude D - (-) - 2- [4- (2,4-dichlorophenoxy) phenoxy] propionic acid thioamide. After recrystallization from ethanol, pale yellow crystals of mp 153-153.5 ° C., [α] D -15.4 ° are obtained.

In analoger Weise werden erhalten :

Figure imgb0037
Figure imgb0038
Figure imgb0039
Figure imgb0040
Figure imgb0041
Figure imgb0042
Figure imgb0043
Figure imgb0044
Figure imgb0045
Figure imgb0046
Figure imgb0047
 The following are obtained in an analogous manner:
Figure imgb0037
Figure imgb0038
Figure imgb0039
Figure imgb0040
Figure imgb0041
Figure imgb0042
Figure imgb0043
Figure imgb0044
Figure imgb0045
Figure imgb0046
Figure imgb0047

Biologische beispieleBiological examples

Die optisch aktiven D-(+)-Verbindungen (im einzelnen s. Tabellen) wurden in Freilandversuchen im Vergleich zu den entsprechenden Racematen im Nachauflaufverfahren gegen verschiedene Schadgräser geprüft. Die Parzellengrößen lagen bei 5 bzw. 10 m2 ; es wurde mit 3- bis 4-facher Wiederholung gearbeitet. Die Verbindungen wurden als Emulsionskonzentrate formuliert und in verschiedenen Aufwandmengen je ha bei einem Wasseraufwand von 500 I/ha ausgebracht, wobei die Flüssigkeitsmenge, auf 1 ha bezogen, jeweils 500 I betrug.The optically active D - (+) compounds (in detail see tables) were tested in field tests in comparison to the corresponding racemates in a post-emergence method against various harmful grasses. The plot sizes were 5 or 10 m 2 ; it was worked with 3 to 4 times repetition. The compounds were formulated as emulsion concentrates and applied in various application rates per hectare at a water rate of 500 l / ha, the amount of liquid, based on 1 ha, being 500 l each.

Die Wirksamkeit der Produkte wurde 30-35 Tage nach der Behandlung mittels « BEA-Schema 1-9 » (Biologische Bundesanstalt, Braunschweig) festgestellt, wobei 1 eine 100 %ige Wirkung und 9 keinerlei Wirkung bedeutet. Bei den Kulturpflanzen bedeutet 1 keine Schädigung und 9 eine totale Schädigung der Pflanzen. Die Kulturpflanzenverträglichkeit wurde außerdem zum ersten Mal bereits eine Woche nach der Behandlung bonitiert.The effectiveness of the products was determined 30-35 days after the treatment using «BEA-Scheme 1-9» (Biological Federal Institute, Braunschweig), where 1 means 100% activity and 9 means no activity. In the case of crop plants, 1 means no damage and 9 means total damage to the plants. Crop tolerance was also assessed for the first time one week after the treatment.

Die in der Tabelle angegebenen ED95-bzw. ED98-Werte geben an, bei welcher Wirkstoffdosis/ha 95 % bzw. 98 % der Schadpflanzen abgetötet werden (ED-« effective dose »).The ED 95 or ED 98 values indicate the active substance dose / ha at which 95% or 98% of the harmful plants are killed (ED “effective dose”).

Beispiel 1example 1

Bekämpfung von Ackerfuchsschwanz (Alopecurus myosuroides) in Zuckerrüben im Nachauflaufverfahren.Control of foxtail (Alopecurus myosuroides) in sugar beet using the post-emergence method.

Zum Zeitpunkt der Behandlung befanden sich die Zuckerrüben im 6-8 Blatt-Stadium. Die ED-Werte sind in Tabelle I angegeben.

Figure imgb0048
At the time of treatment, the sugar beets were in the 6-8 leaf stage. The ED values are given in Table I.
Figure imgb0048

Die Wirkstoffeinsparung liegt somit bei 40 bzw. 43 % im Vergleich zum Racemat. An den behandelten Zuckerrüben trat zu keinem Zeitpunkt Phytotoxis auf.The active ingredient saving is therefore 40 or 43% compared to the racemate. No phytotoxis occurred on the treated sugar beets at any time.

Beispiel 2Example 2

Bekämpfung von Hühnerhirse (Echinochloacrus galli) in Zuckerrüben (4-6-Blattstadium) im Nachauflaufverfahren (Ergebnis siehe Tabelle II) :

Figure imgb0049
Control of millet (Echinochloacrus galli) in sugar beets (4-6 leaf stage) in the post-emergence process (result see Table II):
Figure imgb0049

Die Einsparung an Wirkstoff bei gleichem Bekämpfungserfolg beträgt somit im Vergleich zum Racemat 38 bzw. 41 %. An der Zuckerrübe trat kein Kulturschaden auf.Compared to the Racemat, the saving in active ingredient with the same control success is 38 or 41%. No crop damage occurred on the sugar beet.

Beispiel 3Example 3

Bekämpfung von Flughafer (Avena fatua) und Ackerfuchsschwanz (Alopecurus myosuroides) in Zuckerrüben (6-Blattstadium) im Nachauflaufverfahren (Ergebnis siehe Tabelle 111)

Figure imgb0050
Control of wild oats (Avena fatua) and arable foxtail (Alopecurus myosuroides) in sugar beets (6-leaf stage) using the post-emergence method (result see Table 111)
Figure imgb0050

Die Einsparung an Wirkstoff bei gleichem Bekämpfungserfolg beträgt somit im Verhältnis zum Racemat 45 %. An der Kulturpflanze trat keine Phytotoxis auf.The saving in active ingredient with the same control success is thus 45% in relation to the racemate. No phytotoxis occurred on the crop.

Beispiel 4Example 4

Bekämpfung von Flughafer und Ackerfuchsschwanz in Zuckerrüben (6-Blattstadium) im Nachauflaufverfahren (Ergebnis siehe Tabelle IV).

Figure imgb0051
Control of oats and foxtail in sugar beet (6-leaf stage) in the post-emergence process (result see Table IV).
Figure imgb0051

Die Wirkstoffeinsparung bei der Ackerfuchsschwanzbekämpfung beträgt somit im Verhältnis zum Racemat 41 bzw. 53 %. Bei Flughafer beträgt die Einsparung 62 %.The active ingredient savings in the field foxtail control is therefore 41 or 53% in relation to the Racemat. The savings for airport oats are 62%.

Setzt man unter gleichen Bedingungen den Äthylester aus Beispiel (1) ein, so beträgt die Wirkstoffeinsparung etwa 42 %.

Figure imgb0052
If the ethyl ester from example (1) is used under the same conditions, the active ingredient saving is approximately 42%.
Figure imgb0052

Die Wirkstoffeinsparung beträgt somit 41 % im Vergleich zum Racemat bei gleich hohem Bekämpfungserfolg. An Sommerweizen trat kein Kulturschaden auf.The active ingredient saving is therefore 41% compared to the Racemate with the same high level of control success. There was no cultural damage to summer wheat.

Claims (11)

1. Compounds of the formula I
Figure imgb0079
where
R is a group of the formulae
Figure imgb0080
or
Figure imgb0081
 in which
R1 is hydrogen, halogen or CF3,
R2 is hydrogen, C1-C4-alkyl, halogen or NO2, with the proviso that when R is a radical of the formulae II, III or VI, R1 is other than hydrogen,
Z is a group of the formulae
Figure imgb0082
in which
R3 is H, (C1-C12)-alkyl, optionally substituted with 1-6 halogen atoms and/or OH, (C1-C6)-alkoxy, (C1-C4)-alkylthio, (C1-C6)-alkoxy-(C2-C6)-alkoxy, halo-(C1-C2)-alkoxy, methoxy-ethoxy-ethoxy, (C1-C4)-alkylamino, D-(C1-C4)-alkylamino, phenyl, oxiranyl or phenoxy, the latter one optionally being mono- or disubstituted with halogen and/or (C1-C4)-alkyl; (C5-C6)-cycloalkyl or halo-(C5-C6)-cycloalkyl ; (C3-C6)-alkenyl, halo-(C3-C6)-alkenyl or (C5-C6)-cycloalkenyl, (C3-C4)-alkinyl, optionally mono- or disubstituted with (C1-C6)-alkyl, phenyl, halogen or (C1-C2)-alkoxy ; phenyl, optionally mono- to trisubstituted with (C1-C4)-alkyl, (C1-C4)-alkoxy, halogen, NO2 or CF3 ; furfuryl, tetrahydrofurfuryl or a cation equivalent of an organic or inorganic base,
R4 is (C1-C6)-alkyl optionally substituted with (C1-C4)-alkoxy, halogen or phenyl, the latter one optionally being mono- to trisubstituted with (C1-C4)-alkyl or halogen ; (C3-C6)-alkenyl or phenyl optionally mono- to trisubstituted with (C1-C4)-alkyl and/or halogen,
R5 and R6, being identical or different, each are H, (C1-C6)-alkyl, hydroxy-(C1-C6)-alkyl, (C5-C6)-cycloalkyl or phenyl optionally mono- to trisubstituted with (C1-C4)-alkyl, (C1-C4)-alkoxy, halogen or CF3 (with the proviso that not both R5 and R6 are phenyl), or together form a methylene chain having 2, 4 or 5 members, wherein a CH2 group may be substituted by O, NH or N(CH3),
R7 is H or CH3,
R8 is H, CH3 or C2H5,
R9 is H, CH3, C2H5 or phenyl,

with the proviso that in compounds in which R is a group or formula II, R3 can be H or unsubstituted alkyl only if R1 or R2 are CI in para-position.
2. A process for the manufacture of compounds of formula I as claimed in claim 1, which comprises reacting
a)correspondingly substituted phenols or phenolates of the formula
Figure imgb0083
where X is an alkali metal or hydrogen atom, with substituted L-propionic acid esters of the formula
Figure imgb0084
where Y is chlorine, bromine or a sulfonyloxy group,
or
b) when R is a radical of formula III, IV or V, also by reacting compounds of the formula
Figure imgb0085
with correspondingly substituted 2-halo-pyridines, halobenzthiazoles or halo-benzoxazoles ; and, if desired, converting the compounds of the formula I obtained into other compounds of formula I by methods generally known.
3. Herbicidal compositions, containing an active substance of formula I.
4. Use of compounds of the formula I for combating undesirable plant growth.
5. Compound of the formula
Figure imgb0086
6. Compound of the formula
Figure imgb0087
7. Compound of the formula
Figure imgb0088
8. Compound of the formula
Figure imgb0089
9. Compound of the formula
Figure imgb0090
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Families Citing this family (58)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2862490D1 (en) * 1977-08-12 1988-04-21 Ici Plc Phenoxypyridine compound
US4200587A (en) * 1977-11-28 1980-04-29 Hoffmann-La Roche Inc. 2-[P-(p-Substituted phenoxy)phenoxy]propionyl oximes
DE2967674D1 (en) * 1978-02-15 1988-03-10 Ici Plc Herbicidal derivatives of 2-(4(2-pyridyloxy)phenoxy)propane, processes for preparing them, and herbicidal compositions containing them
DE2964580D1 (en) * 1978-03-01 1983-03-03 Ici Plc Herbicidal pyridine compounds and herbicidal compositions containing them
BE879987A (en) * 1978-11-21 1980-05-13 Shell Int Research PHENOXYPHENOXYPROPIONIC ACID DERIVATIVES, PROCESS FOR THE PREPARATION THEREOF, HERBICIDE PREPARATIONS CONTAINING THESE DRY REQUIREMENTS AND METHOD FOR THE PREVENTION OF WEEDS USING THE SAID DERIVATIVES
IT8048925A0 (en) * 1979-06-22 1980-06-10 Sandoz Ag ESTERS OF TETRAHYDRO-2H-2-PYRANYLMETHANOL THEIR PREPARATION AND THEIR USE AS HERBICIDES
NZ194196A (en) * 1979-07-17 1983-07-15 Ici Australia Ltd -(quinoxalin-2-yl(oxy or thio) phen (oxy or ylthio)-alkanoic acid derivatives or precursors
ZA811357B (en) * 1980-03-10 1982-03-31 Hoffmann La Roche Oxime esters
DE3115152A1 (en) * 1981-04-15 1982-12-02 Hoechst Ag, 6000 Frankfurt "HETEROCYCLIC PHENYL ETHERS AND HERBICIDES CONTAINING THEM"
DK220582A (en) * 1981-05-26 1982-11-27 Hoffmann La Roche PROPION ACID AMIDES
DE3319289A1 (en) * 1983-05-27 1984-11-29 Bayer Ag, 5090 Leverkusen OPTICALLY ACTIVE PHENOXYPROPIONIC ACID ESTER
DK305884A (en) * 1983-06-24 1984-12-25 Yamanouchi Pharma Co Ltd PHENOXYDER DERIVATIVE, PROCEDURE FOR PREPARING THEREOF AND PHARMACEUTICAL PREPARATION CONTAINING SUCH DERIVATIVE
US4532328A (en) * 1983-07-14 1985-07-30 The Dow Chemical Company Process for making optically active esters of phenoxyphenoxypropionic acids or pyridyloxyphenoxypropionic acids
AU587366B2 (en) * 1983-07-27 1989-08-17 Imperial Chemical Industries Plc Process for producing optically active aryloxypropionic acids and derivatives thereof
US4550192A (en) * 1983-09-01 1985-10-29 The Dow Chemical Company Fluorophenoxyphenoxypropionates and derivatives thereof
US4642338A (en) * 1983-09-01 1987-02-10 The Dow Chemical Company Fluorophenoxyphenoxypropionates and derivatives thereof
DE3415069A1 (en) * 1983-11-19 1985-05-30 Hoechst Ag, 6230 Frankfurt HERBICIDAL AGENTS
DE3502266A1 (en) * 1985-01-24 1986-08-07 Bayer Ag, 5090 Leverkusen OPTICALLY ACTIVE PHENOXYPROPIONIC ACID DERIVATIVES
DE3680212D1 (en) * 1985-02-14 1991-08-22 Ciba Geigy Ag USE OF CHINOLINE DERIVATIVES FOR PROTECTING CROPS.
JP2559699B2 (en) * 1985-03-16 1996-12-04 ザ ウエルカム フアウンデ−シヨン リミテツド Novel aryl derivative
GB8531839D0 (en) * 1985-12-30 1986-02-05 Wellcome Found Aryl derivatives
JPS61249954A (en) * 1985-04-26 1986-11-07 Aguro Kanesho Kk Propionic acid derivative
US4857101A (en) * 1985-12-06 1989-08-15 Rohm And Haas Company Method of selectively controlling weeds in crops of cereals
US4790868A (en) * 1986-03-17 1988-12-13 Ppg Industries, Inc. Herbicidally active substituted phenoxy or phenylthio benzoxazolone (or benzthiazolone) compounds
US4746351A (en) * 1986-05-12 1988-05-24 Ppg Industries, Inc. Herbicidally active substituted phenoxy benzoxazole (or benzothiazole)
CH679396A5 (en) * 1986-06-12 1992-02-14 Ciba Geigy Ag
US5207819A (en) * 1987-04-20 1993-05-04 Agro-Kanesho Co., Ltd Phenoxypropionic acid ester derivatives
BR8801855A (en) * 1987-04-20 1988-11-22 Agro Kanesho Co Ltd HERBICIDE COMPOSITION UNDERSTANDING AS A ACTIVE INGREDIENT A PHENOXYPROPIONIC ACID DERIVATIVE DERIVATIVE AND PROCESS FOR THE PRODUCTION OF PHENOXYPROPIONIC ACER DERIVATIVES
US4786731A (en) * 1987-08-05 1988-11-22 The Dow Chemical Company Resolution of enantiomers of 2-(phenyl or phenoxy/propionic acids using optically active alkanolamines
US4786732A (en) * 1987-08-05 1988-11-22 The Dow Chemical Company Resolution of enantiomers of 2-(4-aryloxyphenoxy) propionic acids by liquid chromatography with a chiral eluent
US4789744A (en) * 1987-08-05 1988-12-06 The Dow Chemical Company Process for the resolution of enantiomeric aryloxyphenoxy propionates
US4935522A (en) * 1988-03-21 1990-06-19 Hoechst Celanese Corporation Process for producing ethyl 2-[4'-(6"-chloro-2"-benzoxazolyloxy)phenoxy]propionate
US4897481A (en) * 1988-05-31 1990-01-30 The Dow Chemical Company Process for the minimization of racemization in the preparation of optically active ((aryloxy)phenoxy)propionate herbicides
US4831147A (en) * 1988-07-05 1989-05-16 The Dow Chemical Company Resolution of enantiomers of herbicidal 2-(4-aryloxyphenoxy) propionates by chiral two-phase extraction
US5012017A (en) * 1988-08-18 1991-04-30 Dowelanco Phenoxyphenoxypropionates, intermediates thereof and methods of preparation
DE3902372A1 (en) * 1989-01-27 1990-08-02 Hoechst Ag METHOD FOR PRODUCING D ((ARROW UP) + (ARROW UP)) - 2- (4-ACETYLPHENOXY) - PROPIONIC ACID ESTERS
EP0383613A3 (en) * 1989-02-16 1991-04-03 Tosoh Corporation Optically active lactate, derivatives thereof and processes of producing same
US5258521A (en) * 1989-07-26 1993-11-02 Tosoh Corporation Process of producing optically active propionic acid ester derivatives
JPH0832612B2 (en) * 1989-10-18 1996-03-29 ヘキスト・アクチェンゲゼルシャフト Herbicidal active substance combination agent
US5811374A (en) * 1991-02-07 1998-09-22 Bayer Aktiengesellschaft 3-aryl-pyrrolidine-2,4-dione derivatives
DE4126999A1 (en) * 1991-08-16 1993-02-18 Basf Ag HERBICIDE AGENT, CONTAINING 3-AMINOBENZO (B) THIOPHENE AS ANTIDOTS
ES2112284T3 (en) * 1991-09-14 1998-04-01 Hoechst Schering Agrevo Gmbh SELECTIVE HERBICIDAL AGENTS IN THE FORM OF CONCENTRATED MICROEMULSIONS.
DE4131585A1 (en) * 1991-09-23 1993-03-25 Bayer Ag (ALPHA) - (5-DICHLORPHENOXY-NAPHTHALIN-L-YL-OXY) PROPIONE ACID DERIVATIVES
ES2108855T3 (en) * 1992-07-21 1998-01-01 Ciba Geigy Ag DERIVATIVES OF OXAMIC ACID AS HYPOCHOLESTEREMIC AGENTS.
JPH06179646A (en) * 1992-12-15 1994-06-28 Tokuyama Soda Co Ltd Cyanoketone derivative
US5756425A (en) * 1996-09-09 1998-05-26 Ash; David Fluazifop-butyl formulation and process for the selective control of Bermuda and other grasses in Bentgrass and St. Augustinegrass turf
US6600048B2 (en) 1998-07-25 2003-07-29 Dongbu Hannong Chemical Co., Ltd. Herbicidal phenoxypropionic acid N-alkyl-N-2-fluorophenyl amide compounds
KR100314776B1 (en) * 1998-07-25 2001-11-17 우종일 Herbicidal phenoxypropionic acid N-alkyl-N-2-fluorophenyl amides
ATE250855T1 (en) 1999-08-03 2003-10-15 Dongbu Hannong Chemical Co Ltd HIGHLY SELECTIVE HERBICIDES PHENOXYPROPIONIC ACID-ALKOXYCARBONYLANILIDES AND METHOD FOR THE PRODUCTION THEREOF
KR100419853B1 (en) * 2000-05-04 2004-02-25 동부한농화학 주식회사 Optically active herbicidal (R)-phenoxypropionic acid-N-methyl-N-2-fluorophenyl amides
KR100552133B1 (en) * 2002-06-26 2006-02-14 한국화학연구원 A process for R-Aryloxypropionic acid ester derivatives
EP2052607A1 (en) 2007-10-24 2009-04-29 Bayer CropScience AG Herbicide combination
DE102008037622A1 (en) 2008-08-14 2010-02-25 Bayer Cropscience Ag Herbicide combination with dimethoxytriazinyl-substituted difluoromethanesulfonylanilides
CN101372481B (en) * 2008-08-19 2012-03-14 江苏中意化学有限公司 Method for synthesizing 6-chloro-2-(p-hydroxyl)-phenoxy-benzoxazole
US8186436B2 (en) * 2009-09-10 2012-05-29 Warren Carlos Thermal insulating packer fluid
CN102351808B (en) * 2011-09-06 2013-07-03 江苏中旗作物保护股份有限公司 New method for synthesizing fenoxaprop-P-ethyl
EP3222143A1 (en) 2016-03-24 2017-09-27 Bayer CropScience Aktiengesellschaft Use of certain herbicide combinations based on iodosulfuron in teff plants
CN106699649B (en) * 2016-12-15 2019-10-08 三峡大学 The hexa-atomic aryloxyphenoxy of 2-() acid derivative and its application

Family Cites Families (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA683033A (en) * 1964-03-24 Frommer Werner OPTICALLY-ACTIVE .alpha.-ALKYL-SUBSTITUTED PHENOXYACETIC ACIDS AND PROCESSES FOR PRODUCING THE SAME
CH2246A (en) * 1890-05-18 1890-09-15 J Pontius Petroleum container with protective device
US2668104A (en) * 1951-08-23 1954-02-02 Dow Chemical Co Plant growth regulant compositions comprising chloroaryloxyacetic acids and esters thereof
DE2223894C3 (en) * 1972-05-17 1981-07-23 Hoechst Ag, 6000 Frankfurt Herbicidal agents based on phenoxycarboxylic acid derivatives
IL45894A0 (en) * 1973-10-25 1974-12-31 Ciba Geigy Ag New aryl alkyl ethers,their preparation and their use in pest control
DE2417487C2 (en) * 1974-04-10 1983-01-20 Hoechst Ag, 6000 Frankfurt Benzylphenoxyalkanecarboxylic acids, their derivatives and processes for their preparation
DE2433067B2 (en) * 1974-07-10 1977-11-24 a- [4-(4" Trifluormethylphenoxy)-phenoxy] -propionsäuren und deren Derivate, Verfahren zu ihrer Herstellung und diese enthaltende herbizide Mittel Hoechst AG, 6000 Frankfurt ALPHA SQUARE BRACKETS ON 4- (4 'TRIFLUORMETHYLPHENOXY) -PHENOXY SQUARE BRACKETS ON PROPIONIC ACIDS AND THEIR DERIVATIVES, METHOD FOR THEIR PRODUCTION AND HERBICIDAL AGENTS CONTAINING THESE
CS185694B2 (en) * 1974-07-17 1978-10-31 Ishihara Sangyo Kaisha Herbicidal agent
DK154074C (en) * 1974-10-17 1989-02-27 Ishihara Sangyo Kaisha ALFA- (4- (5 OR 3.5 SUBSTITUTED PYRIDYL-2-OXY) -PHENOXY) -ALKANE CARBOXYLIC ACIDS OR DERIVATIVES THEREOF USED AS HERBICIDES, HERBICIDES AND PROCEDURES
US4106925A (en) * 1975-11-20 1978-08-15 Ishihara Sangyo Kaisha Ltd. Novel herbicidally active, nuclear-substituted phenoxy-phenoxy-alkanecarboxylic acid derivatives and use thereof for controlling grass-like weeds
JPS5283640A (en) * 1976-01-01 1977-07-12 Hoechst Ag Benzyllphenoxyalkane carboxylate and derivatives thereof
DE2601548C2 (en) * 1976-01-16 1984-01-26 Hoechst Ag, 6230 Frankfurt 2- [4- (2'-chloro-4'-bromophenoxy) phenoxy] propionic acid and derivatives and herbicidal agents containing them
JPS52131539A (en) * 1976-04-13 1977-11-04 Ishihara Sangyo Kaisha Ltd Phenoxyphenoxypropionic acid derivatives and herbicides
JPS52128220A (en) * 1976-04-20 1977-10-27 Ishihara Sangyo Kaisha Ltd Herbicides
DE2617804C2 (en) * 1976-04-23 1985-01-24 Hoechst Ag, 6230 Frankfurt 2- (4-Phenoxy phenoxy) propionic acid derivatives and their use as herbicides
DE2623558C2 (en) * 1976-05-26 1984-12-06 Hoechst Ag, 6230 Frankfurt 2- [4'-Phenoxyphenoxy] propionic acid derivatives, process for their preparation and herbicidal compositions containing them
DE2640730C2 (en) * 1976-09-10 1983-08-25 Hoechst Ag, 6230 Frankfurt Benzoxazolyloxy and benzothiazolyloxyphenoxy compounds and herbicidal agents containing them
IT1091580B (en) * 1977-01-31 1985-07-06 Hoffmann La Roche ESTERS OF SUBSTITUTED PHENOXY-ALCAN-CARBOXYLIC ACIDS
US4090866A (en) * 1977-03-14 1978-05-23 O. M. Scott & Sons Company Process for the selective control of tall fescue in turf
CA1247625A (en) * 1977-07-22 1988-12-28 Howard Johnston Trifluoromethyl pyridinyloxyphenoxy propanoic acids and propanols and derivatives thereof and methods of herbicidal use
DE2862490D1 (en) * 1977-08-12 1988-04-21 Ici Plc Phenoxypyridine compound
US4200587A (en) * 1977-11-28 1980-04-29 Hoffmann-La Roche Inc. 2-[P-(p-Substituted phenoxy)phenoxy]propionyl oximes
BR7808722A (en) * 1977-12-23 1979-11-20 Ici Ltd HERBICIDAL COMPOUNDS AND COMPOSITES, PROCESS FOR THE CONTROL OF GRASS Weed, PROCESS FOR THE EFFECTIVE CONTROL OF GRASS WEAK IN THE PRESENCE OF A BROAD LEAF HARVEST AND PROCESS FOR THE PREPARATION OF A COMPOUND
DE2964580D1 (en) * 1978-03-01 1983-03-03 Ici Plc Herbicidal pyridine compounds and herbicidal compositions containing them
DE2963229D1 (en) * 1978-06-29 1982-08-19 Ciba Geigy Ag Herbicidal, optically active r(+)-dichloropyridyloxy-alpha-phenoxy-propionic acid-propargylesters, process for their preparation and their use in herbicidal compositions
BE879987A (en) * 1978-11-21 1980-05-13 Shell Int Research PHENOXYPHENOXYPROPIONIC ACID DERIVATIVES, PROCESS FOR THE PREPARATION THEREOF, HERBICIDE PREPARATIONS CONTAINING THESE DRY REQUIREMENTS AND METHOD FOR THE PREVENTION OF WEEDS USING THE SAID DERIVATIVES

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AT368357B (en) 1982-10-11
RO75478B (en) 1984-05-30
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US4531969A (en) 1985-07-30
ZA787210B (en) 1979-12-27
HU182883B (en) 1984-03-28
DK579078A (en) 1979-06-25
CH650493A5 (en) 1985-07-31
PL122180B1 (en) 1982-06-30
MX6673A (en) 1993-12-01
BE873844A (en) 1979-05-16
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FR2447366B1 (en) 1984-11-16
US5712226A (en) 1998-01-27
IL56283A0 (en) 1979-03-12
EP0002800B2 (en) 1991-10-09
AU527127B2 (en) 1983-02-17
AU4284978A (en) 1979-06-28
IL56283A (en) 1987-09-16
CA1268475A (en) 1990-05-01
FR2447366A1 (en) 1980-08-22
MX5673E (en) 1983-12-08
IE47703B1 (en) 1984-05-30
PL212111A1 (en) 1980-02-11
DD141403A5 (en) 1980-04-30
DK156511B (en) 1989-09-04
ES476100A1 (en) 1979-04-16
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DE2861428D1 (en) 1982-01-28
RO79065A (en) 1982-06-25
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CS204959B2 (en) 1981-04-30
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RO75478A (en) 1984-04-12
GR65233B (en) 1980-07-30
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